Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents

ABSTRACT

Compounds of formula I 
       A-B  (I),
 
     wherein A is a radical selected from the group consisting of formulae A 1  to A 8 : 
     
       
         
         
             
             
         
       
     
     wherein the arrow denotes the point of attachment to the radical B; and
 
B is a radical selected from the group consisting of formulae B 1  to B 11 :
 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein the arrow denotes the point of attachment to the radical A; and wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula I can be used as insecticides and can be prepared in a manner known per se.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of Ser. No. 17/068,334, filed Oct. 12,2020, which is a continuation of U.S. application Ser. No. 14/898,597,filed Dec. 15, 2015, which is a 371 National Stage application ofInternational Application No. PCT/EP2014/062946, filed Jun. 19, 2014,which claims priority to EP 13174698.4, filed Jul. 2, 2013, EP13176263.5, filed Jul. 12, 2013, EP 13197069.1, filed Dec. 13, 2013; andInternational Patent Application No. PCT/CN2014/076736, filed May 4,2014, the contents of which applications are herein incorporated byreference.

The present invention relates to insecticidally active heterocyclicsulfur containing derivatives, to processes for their preparation, tocompositions comprising those compounds, and to their use forcontrolling animal pests (including arthropods and in particular insectsor representatives of the order Acarina).

Heterocyclic compounds with pesticidal action are known and described,for example, in WO 2009/131237, WO 2011/043404, WO 2011/040629, WO2010/125985, WO 2012/086848, WO 2013/018928, WO 2013/191113, WO2013/180193 and WO 2013/180194.

There have now been found novel heterocyclic derivatives with pesticidalproperties.

The present invention accordingly relates to compounds of formula I,

A-B  (I),

wherein A is a radical selected from the group consisting of formulae A₁to A₈:

wherein the arrow denotes the point of attachment to the radical B; andB is a radical selected from the group consisting of formulae B₁ to B₁₁:

wherein the arrow denotes the point of attachment to the radical A;whereinL₁ is methylene or a direct bond;V₀ nitrogen or CR₅;V₁ is nitrogen or CR₂₀; V₂ is nitrogen or CR₂₁; V₃ is nitrogen or CR₂₂;V₄ is nitrogen or CR₂₃;V₅ is nitrogen or CR₂₄; V₆ is nitrogen or CR₂₅; V₇ is nitrogen or CR₂₆;V₈ is nitrogen or CR₂₇;V₉ is nitrogen, or CR₂₈V₁₀ is nitrogen or CR₂₉; V₁₁ is nitrogen or CR₃₀;G₁ is nitrogen or CR₃₁;G₂ is nitrogen or CR₃₂;G₃ is —NR₃₅, an oxygen atom or a sulfur atom;G₄ is nitrogen or CR₃₃;G₅ is nitrogen or CR₃₄;J₁, J₂, J₃ together form together a 5 membered heterocyclic ring, whichcan be saturated or unsaturated, containing one or two atoms selectedfrom the group consisting of nitrogen, oxygen and sulfur, which ring canbe mono- or polysubstituted by substituents selected from the groupconsisting of C₁-C₆alkyl, halogen and or C₁-C₆haloalkyl, with theproviso that if the ring contains two oxygen atoms, or two sulfur atoms,they are separated by one carbon atom;R₁ and R₂ are the same or different and each represents hydrogen,halogen, C₁-C₆alkyl or C₁-C₆haloalkyl;R₃ is a C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group which can bemono- or polysubstituted by substituents selected from the groupconsisting of C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy,C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulfanyl, C₁-C₆ alkylsulfinyl,C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl,C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl,C₂-C₆haloalkoxycarbonyl, cyano, hydroxy, halogen, C₃-C₆ cycloalkyl, saidC₃-C₆cycloalkyl itself can be mono- or polysubstituted by substituentsselected from halogen and C₁-C₃alkyl; and by a 5- or 6-memberedheterocyclic group, which can be mono- or polysubstituted bysubstituents selected from the group consisting of C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulfanyl,C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,C₁-C₆alkylamino, C₁-C₆haloalkylamino, C₂-C₈dialkylamino,C₂-C₈halodialkylamino, halogen, cyano and nitro;or R₃ is —CO₂R₃₆, —C(O)R₃₆ or hydrogen;or R₃ is C₃-C₆cycloalkyl, which can be mono- or polysubstituted bysubstituents selected from the group consisting of C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy and halogen;or R₃ is a 5- or 6-membered heterocyclic group, which can be mono- orpolysubstituted by substituents selected from the group consisting ofC₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₆alkylsulfanyl, C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl,C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl,C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl,C₂-C₆haloalkoxycarbonyl, C₁-C₆alkylamino, C₁-C₆haloalkylamino,C₂-C₈dialkylamino, C₂-C₈halodialkylamino, halogen, cyano and nitro;R₃₅ is hydrogen, C₁-C₆alkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆ alkynyloxy,C₂-C₆haloalkynyloxy, C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulfanyl,C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylsulfonyl, C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, cyano,hydroxy, halogen and C₃-C₆cycloalkyl, said C₃-C₆cycloalkyl itself can bemono- or polysubstituted by substituents selected from halogen andC₁-C₃alkyl; or an N-oxide thereof;R₄, R₅, R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, R₂₉ and R₃₀ are thesame or different and represents cyano, nitro, halogen, hydroxy,C₁-C₆alkenyloxy, C₁-C₆haloalkoxy, —C(O)R₃₆—C(O)R₃₆ or hydrogen; orC₁-C₆alkyl which can be mono- or polysubstituted by substituentsselected from the group consisting of cyano, halogen, hydroxy,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy,C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy, C₁-C₆alkylsulfanyl,C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,cyano, hydroxy, halogen and C₃-C₆cycloalkyl, said cycloalkyl itself canbe substituted by substituents selected from the group consisting ofhalogen and C₁-C₃alkyl, or representsa phenyl group which can be mono or polysubstituted by substituentsselected from the group consisting of C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulfanyl,C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,C₁-C₆alkylamino, C₁-C₆haloalkylamino, C₂-C₈dialkylamino,C₂-C₈halodialkylamino, halogen, cyano, and nitro;R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈ and R₁₉ arethe same or different and represents C₁-C₆alkyl, C₁-C₆haloalkyl orhydrogen, and the group CR₁₃R₁₄ can additionally be a carbonyl groupC═O;R₃₁, R₃₂, R₃₃, R₃₄ and R₄₀ are the same or different and representsC₁-C₆ alkyl, C₁-C₆haloalkyl, —OR₇, —S(O)_(n)R₃₆, —NR₃₆R₃₇, —CO₂R₃₆,—C(O)R₃₆, cyano, nitro, halogen or hydrogen;R₃₆ and R₃₇ are the same or different and represents hydrogen,C₁-C₆alkyl which can be mono- or polysubstituted by substituentsselected from C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy, C₁-C₆alkylsulfanyl, C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl,C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl,C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl,C₂-C₆haloalkoxycarbonyl, cyano, hydroxy, halogen and C₃-C₆ cycloalkyl,wherein said C₃-C₆ cycloalkyl can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen andC₁-C₃alkyl; orR₃₆ and R₃₇ are the same or different and representsa phenyl group which can be mono- or polysubstituted by substituentsselected from the group consisting of C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulfanyl,C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,C₁-C₆alkylamino, C₁-C₆haloalkylamino, C₂-C₈dialkylamino,C₂-C₈halodialkylamino, halogen, cyano, and nitro;each m independently represents 0, 1 or 2, and n represents 0, 1 or 2,with the provisos that:

-   -   a) in —S(O)_(n)R₃₆, R₃₆ is hydrogen when n is 0;    -   b) if B is B₁, then A is different from A₂, A₃ and A₅;    -   c) if A is A₁, then B is different from B₁, B₇, B₈, B₉ and B₁₀;    -   d) if A is A₅, then B is different from B₁₀;        as well as agrochemically acceptable salts, enantiomers,        diastereomers, tautomers, and N-oxides of those compounds.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, withstrong organic carboxylic acids, such as C₁-C₄alkanecarboxylic acidswhich are unsubstituted or substituted, for example by halogen, forexample acetic acid, such as saturated or unsaturated dicarboxylicacids, for example oxalic acid, malonic acid, succinic acid, maleicacid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids,for example ascorbic acid, lactic acid, malic acid, tartaric acid orcitric acid, or such as benzoic acid, or with organic sulfonic acids,such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted orsubstituted, for example by halogen, for example methane- orp-toluenesulfonic acid. Compounds of formula I which have at least oneacidic group can form, for example, salts with bases, for examplemineral salts such as alkali metal or alkaline earth metal salts, forexample sodium, potassium or magnesium salts, or salts with ammonia oran organic amine, such as morpholine, piperidine, pyrrolidine, a mono-,di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, forexample mono-, di- or triethanolamine.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl,hexyl, nonyl, decyl and their branched isomers. Alkoxy, alkenyl andalkynyl radicals are derived from the alkyl radicals mentioned. Thealkenyl and alkynyl groups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy groups preferably have a preferred chain length of from 1 to 6carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also theisomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl,isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferablymethoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have achain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example,fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy,2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferablydifluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 6 carbonatoms. Alkylthio is, for example, methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio ortert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is,for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl,isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl,tert-butylsulfinyl; preferably methylsulfinyl and ethylsulphinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl orethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino,isopropylamino or the isomeric butylamines. Dialkylamino is, forexample, dimethylamino, methylethylamino, diethylamino,n-propylmethylamino, dibutylamino and diisopropylamino. Preference isgiven to alkylamino groups having a chain length of from 1 to 4 carbonatoms.

Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbonatoms.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, forexample cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Phenyl,also as part of a substituent such as phenoxy, benzyl, benzyloxy,benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. Inthis case, the substituents can be in ortho, meta and/or para position.The preferred substituent positions are the ortho and para positions tothe ring attachment point.

In the context of this invention “mono- to polysubstituted” in thedefinition of the substituents, means typically, depending on thechemical structure of the substituents, monosubstituted to seven-timessubstituted, preferably monosubstituted to five-times substituted, morepreferably mono-, double- or triple-substituted.

“5-membered heterocyclic” in the present invention means a 5-memberedaromatic heterocyclic group or 5-membered non-aromatic heterocyclicgroup, and the “6-membered heterocyclic” means a 6-membered aromaticheterocyclic group or a. 6-membered non-aromatic heterocyclic group.Accordingly, a “5- or 6-membered heterocyclic group” in the presentinvention means a 5- or 6-membered aromatic heterocyclic group, or a 5-or 6-membered non-aromatic heterocyclic group.

“5- or 6-membered heterocyclic group, which can be substituted” in thepresent invention means a heterocyclic group, wherein the hydrogenatom(s) bound to the carbon atom(s), nitrogen atom(s) and/or sulfuratom(s) is/are optionally substituted by one or more atoms or groupsselected from a pre-defined list, wherein the group has two or moreatoms or groups selected from a pre-defined list, these atoms or groupsare the same or different from each other. In context of an N atom or Satom, when it's oxidized to form an N oxide or sulfone and sulfoxiderespectively, the oxidised analog is not substituted; however, such ananalog is within the scope of the invention. Examples of 5- or6-membered heterocyclic group, which can be substituted includepyrrolidin-1-yl group, a 3,3,4,4-tetrafluoropyrrolidin-1-yl group, atetrahydrofuran-2-yl group, a piperidyl group, a morpholyl group, athiomorpholyl group, and the like.

Examples of a 5- or 6-membered aromatic heterocyclic groups, which canbe substituted, are 2-pyrroly, 2-furyl group, 3-furyl, 5-pyrazolyl, a4-pyrazolyl, 1-pyrroly, I-methyl-2-pyrroly, 2-methylsulfanyl-1-pyrroly,2-methylsulfinyl-1-pyrroly, 2-methylsulfonyl-1-pyrroly, a2-methylamino-1-pyrroly group, a 2-dimethylamino-1-pyrroly group, a5-bromo-2-furyl, a 5-nitro-2-furyl group, a 5-cyano-2-furyl group, a5-methoxy-2-furyl group, a 5-acetyl-2-furyl, a 5-methoxycarbonyl-2-furylgroup, a 2-methyl-3-furyl group, a 2,5-dimethyl-3-furyl group, a2,4-dimethyl-3-furyl group, a 5-methyl-2-thienyl group, a3-methyl-2-thienyl group, a 1-methyl-3-trifluoromethyl-5-pyrazolylgroup, a 5-chloro-1,3-dimethyl-4-pyrazolyl group, pyrazol-1-yl group, a3-chloro-pyrazol-1-yl group, a 3-bromopyrazol-1-yl group, a4-chloropyrazol-1-yl group, a 4-bromopyrazol-1-yl group, animidazole-1-yl group, a 1,2,4-triazol-1-yl group, a3-chloro-1,2,4-triazol-1-yl group, a 1,2,3,4-tetrazol-1-yl group, a1,2,3,5-tetrazol-1-yl group, a 2-thienyl group, a 3-thienyl group, a3-trifluoromethyl-1,2,4-triazol-1-yl group, a 4-trifluoromethylpyrazol-1-yl group, pyrazinyl group, a 4-pyrimidinyl group, a5-pyrimidinyl group, a 2-pyridyl group, a 3-pyridyl group, a

4-pyridyl group, a 3-fluoro-2-pyridyl group, a 4-fluoro-2-pyridyl group,a 5-fluoro-2-pyridyl group, a 6-fluoro-2-pyridyl group, a 2-pyrimidinylgroup, a 3-chloro-5-trifluoromethylpyridin-2-yl group, a5-trifluoromethylpyridin-2-yl group, and the like.

In a preferred embodiment of the invention, R₃₅ is C₁-C₆alkyl which canbe mono- or polysubstituted by substituents selected from the groupconsisting of C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆ alkynyloxy, C₂-C₆haloalkynyloxy,C₁-C₆alkylsulfanyl, C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl,C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl,C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, cyano, hydroxy, halogen andC₃-C₆cycloalkyl, said C₃-C₆cycloalkyl itself can be mono- orpolysubstituted by substituents selected from halogen and C₁-C₆alkyl; oran N-oxide thereof.

Preferably R₄, R₅, R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, R₂₉, andR₃₀ are the same or different and represents cyano, nitro, halogen,hydroxy, —C(O)R₃₆ or hydrogen; or

C₁-C₆alkyl which can be mono- or polysubstituted by substituentsselected from the group consisting of cyano, halogen, hydroxy,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy,C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy, C₁-C₆alkylsulphanyl,C₁-C₆haloalkylsulphanyl, C₁-C₆ alkylsulphinyl, C₁-C₆haloalkylsulphinyl,C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,cyano, hydroxy, halogen and C₃-C₆cycloalkyl, said cycloalkyl itself canbe substituted by substituents selected from the group consisting ofhalogen and C₁-C₆alkyl; or representsa phenyl group which can be mono or polysubstituted by substituentsselected from the group consisting of C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulphanyl,C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl, C₁-C₆haloalkylsulphinyl,C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,C₁-C₆alkylamino, C₁-C₆haloalkylamino, C₂-C₈dialkylamino,C₂-C₈halodialkylamino, halogen, cyano, and nitro.

Compounds of formula (I) are made up of a combination of a radicalselected from group A and a radical selected from group B.

Accordingly, in an embodiment of the invention, the compound of formula(I) is a radical selected from A and any one radical selected from groupB, such as

-   -   a) radical A₁ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁;    -   b) radical A₂ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁;    -   c) radical A₃ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁₁;    -   d) radical A₄ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁₁;    -   e) radical A₅ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁₁;    -   f) radical A₆ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁₁;    -   g) radical A₇ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁₁; or    -   h) radical A₈ is combined with one radical selected from the        group consisting of the radicals B₁ to B₁₁.

Similarly, in another embodiment, the compound of formula (I) is aradical selected from B and any one radical selected from group A, suchas

-   -   a) radical B₁ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   b) radical B₂ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   c) radical B₃ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   d) radical B₄ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   e) radical B₅ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   f) radical B₆ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   g) radical B₇ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   e) radical B₈ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   f) radical B₉ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈;    -   g) radical B₁₀ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈; or    -   h) radical B₁₁ is combined with one radical selected from the        group consisting of the radicals A₁ to A₈.

In a further embodiment, radical A is selected from any one of thefollowing more specific radicals Q₁ to Q₁₁ from A₁ to A₈, wherein R₁ isas defined in the first aspect:

Further embodiments of the first aspect are set-out in Table Z below:

TABLE Z Combinations of A and B for formula (I) Embodiment E A group Bgroup E1 A₁ B₁ E2 A₁ B₂ E3 A₁ B₃ E4 A₁ B₄ E5 A₁ B₅ E6 A₁ B₆ E7 A₁ B₇ E8A₁ B₈ E9 A₁ B₉ E10 A₁ B₁₀ E11 A₁ B₁₁ E12 A₂ B₁ E13 A₂ B₂ E14 A₂ B₃ E15A₂ B₄ E16 A₂ B₅ E17 A₂ B₆ E18 A₂ B₇ E19 A₂ B₈ E20 A₂ B₉ E21 A₂ B₁₀ E22A₂ B₁₁ E23 A₃ B₁ E24 A₃ B₂ E25 A₃ B₃ E26 A₃ B₄ E27 A₃ B₅ E28 A₃ B₆ E29A₃ B₇ E30 A₃ B₈ E31 A₃ B₉ E32 A₃ B₁₀ E33 A₃ B₁₁ E34 A₄ B₁ E35 A₄ B₂ E36A₄ B₃ E37 A₄ B₄ E38 A₄ B₅ E39 A₄ B₆ E40 A₄ B₇ E41 A₄ B₈ E42 A₄ B₉ E43 A₄B₁₀ E44 A₄ B₁₁ E45 A₅ B₁ E46 A₅ B₂ E47 A₅ B₃ E48 A₅ B₄ E49 A₅ B₅ E50 A₅B₆ E51 A₅ B₇ E52 A₅ B₈ E53 A₅ B₉ E54 A₅ B₁₀ E55 A₅ B₁₁ E56 A₆ B₁ E57 A₆B₂ E58 A₆ B₃ E59 A₆ B₄ E60 A₆ B₅ E61 A₆ B₆ E62 A₆ B₇ E63 A₆ B₈ E64 A₆ B₉E65 A₆ B₁₀ E66 A₆ B₁₁ E67 A₇ B₁ E68 A₇ B₇ E69 A₇ B₈ E70 A₇ B₉ E71 A₇ B₁₀E72 A₇ B₁₁ E73 A₈ B₁ E74 A₈ B₇ E75 A₈ B₈ E76 A₈ B₉ E77 A₈ B₁₀ E78 A₈ B₁₁

In an embodiment of the present invention, a preferred radical A is A₁,A₆, or A₄; especially preferred is A₁ and A₆; in particular A₁.

In another preferred embodiment of the present invention, a preferredradical B is B₁, B₂, B₁₁, B₇, B₈, B₉, B₁₀, B₃ or B₆; especiallypreferred is B₁, B₂, B₁₁, B₇, B₈, B₉, or B₁₀, in particular B₁, B₂, B₁₁,B₇, B₈ or B₉; such as B₁, B₂ or B₁₁.

Accordingly, formula (I) preferably consists of the followingcombinations of radicals A and B:

A group B group A₁ B₁ A₁ B₂ A₁ B₁₁ A₁ B₇ A₁ B₈ A₁ B₉ A₁ B₁₀ A₁ B₃ A₆ B₁A₆ B₂ A₆ B₁₁ A₆ B₇ A₆ B₈ A₆ B₉ A₆ B₁₀ A₆ B₃ A₄ B₁ A₄ B₂ A₄ B₁₁ A₄ B₇ A₄B₈ A₄ B₉ A₄ B₁₀ A₄ B₃

In an embodiment of the present invention, if V₀ in B₁ is CR₅, A isdifferent from A₁. In a preferred embodiment, V₀ in B₁ is CR₅ and A isselected from A₂, A₃, A₄, A₅ and A₆, especially selected from A₄ and A₆.

In an embodiment of the present invention, L₁, in reference to each ofB, is a direct bond.

In another embodiment of the present invention, R₁, in reference to eachof A, is the same or different and each represents hydrogen, halogen,C₁-C₃alkyl or C₁-C₃ haloalkyl; preferably hydrogen, bromine, chlorine,methyl, difluoromethyl or trifluoromethyl.

In another embodiment of the present invention, R₂, in reference to eachof A, is the same or different and each represents, hydrogen, halogen,C₁-C₃alkyl or C₁-C₃haloalkyl; preferably hydrogen.

In another embodiment of the present invention, R₃, in reference to eachof B, is the same or different and each represents C₁-C₃alkyl orC₁-C₃haloalkyl; preferably methyl or ethyl.

In another embodiment of the present invention, R₄, in reference to eachof B, is the same or different and each represents, hydrogen orC₁-C₃alkyl; preferably hydrogen or methyl.

Also preferred are compounds of formula I, represented by a combinationof the 4 “another embodiment” groups mentioned above.

In another embodiment of the present invention, m, in reference to eachof B, is the same or different and each represents 0, 1 or 2; preferably2.

In another embodiment of the present invention, R₆ and R₇, in referenceto each of B, is the same or different and each represents C₁-C₃alkyl orC₁-C₃haloalkyl; preferably methyl.

In another embodiment of the present invention, R₁₀ and R₁₁, inreference to each of B, is the same or different and each represents,hydrogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferably hydrogen or methyl.In a preferred embodiment, R₁₁ is hydrogen and R₁₀ is methyl.

In another embodiment of the present invention, R₁₂, R₁₃, and R₁₄, inreference to each of B, is the same or different and each represents,hydrogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl; preferably hydrogen or methyl.In a preferred embodiment, R₁₃, and R₁₄ are each hydrogen and R₁₂ ismethyl.

In another embodiment of the present invention, R₁₅, R₁₆, R₁₇ and R₁₈,in reference to each of B, is the same or different and each represents,hydrogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl; preferably hydrogen or methyl.In a preferred embodiment, R₁₅, R₁₆, R₁₇ and R₁₈ are each hydrogen.

In another embodiment of the present invention, R₁₉, in reference toeach of B, is the same or different and represents, hydrogen, C₁-C₄alkyl or C₁-C₄ haloalkyl; preferably hydrogen or tert-butyl.

In another embodiment of the present invention, V₁, in reference to eachof B, is the same or different and represents CH or N.

In another embodiment of the present invention, V₀, in reference to eachof B, is the same or different and represents CH or N.

In another embodiment of the present invention, V₂, in reference to eachof B, is the same or different and represents, CR_(21′), where R_(21′),in reference to each of B, is the same or different and represents,hydrogen, halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl, or phenyl or4-trifluoromethylphenyl, preferably hydrogen, chlorine, bromine ortrifluoromethyl.

In another embodiment of the present invention, V₃, in reference to eachof B, is the same or different and represents, CR_(22′), where R_(22′),in reference to each of B, is the same or different and represents,hydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl, preferably hydrogen,chlorine, bromine or trifluoromethyl.

In another embodiment of the present invention, V₄, in reference to eachof B, is the same or different and represents, N or CR_(23′), whereR_(23′), in reference to each of B, is the same or different andrepresents, hydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferablyV₄ represents N or CH.

In another embodiment of the present invention, V₅, in reference to eachof B, is the same or different and represents, N or CR_(24′), where R₂₄,in reference to each of B, is the same or different and represents,hydrogen, halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; preferably V₅represents CH.

In another embodiment of the present invention, V₆, in reference to eachof B, is the same or different and represents, N or CR_(25′), where R₂₅,in reference to each of B, is the same or different and represents,hydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferably V₅represents N or CH.

In another embodiment of the present invention, V₇, in reference to eachof B, is the same or different and represents, N or CR_(26′), whereR_(26′), in reference to each of B, is the same or different andrepresents, hydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferablyV₇ represents N, CH, C-chlorine, C-bromine or C—CF₃.

In another embodiment of the present invention, V₈, in reference to eachof B, is the same or different and represents, N or CR₂₇, where R_(27′),in reference to each of B, is the same or different and representshydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferably V₈represents CH.

In another embodiment of the present invention, V₉, in reference to eachof B, is the same or different and represents, N or CR₂₈, where R_(28′),in reference to each of B, is the same or different and representshydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferably V₉represents N or CH.

In another embodiment of the present invention, V₁₀, in reference toeach of B, is the same or different and represents, N or CR_(29′), whereR_(29′), in reference to each of B, is the same or different andrepresents hydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferablyV₉ represents N or CH.

In another embodiment of the present invention, V₁₁, in reference toeach of B, is the same or different and represents N or CR₃₀, where R₃₀,in reference to each of B, is the same or different and representshydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferably V₉represents N or CH.

In another embodiment of the present invention, G₁, in reference to eachof A, is the same or different and represents N or CR_(31′), whereR_(31′), in reference to each of A, is the same or different andrepresents hydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferablyG₁ represents N or CH.

In another embodiment of the present invention, G₂, in reference to eachof A, is the same or different and represents N or CR_(32′), whereR_(32′), in reference to each of A, is the same or different andrepresents hydrogen, halogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferablyG₂ represents N or CH.

In another embodiment of the present invention, G₃, in reference to eachof A, is the same or different and represents oxygen, sulfur or NR₃₅,where R₃₅ is N-methyl, in reference to each of A, is the same ordifferent and represents C₁-C₃alkyl or C₁-C₃haloalkyl; preferably G₃represents oxygen, sulfur, or N—CH₃.

In another embodiment of the present invention, G₄, in reference to eachof A, is the same or different and represents N or CR_(33′), whereR_(33′), in reference to each of A, is the same or different andrepresents C₁-C₃alkyl or C₁-C₃haloalkyl; preferably G₄ represents N orN—CH₃.

In another embodiment of the present invention, G₅, in reference to eachof A, is the same or different and represents N or CR_(34′), whereR_(34′), in reference to each of A, is the same or different andrepresents hydrogen, C₁-C₃alkyl or C₁-C₃haloalkyl; preferably G₅represents N or N—CH₃.

In another embodiment of the present invention, J₁, in reference to eachof radical A₄, is N.

In another embodiment of the present invention, J₂, in reference to eachof radical A₄, is CH, C₁-C₃ alkyl or C₁-C₃ haloalkyl, such as CH, C—CH₃,or C—CF₃.

In another embodiment of the present invention, J₃, in reference to eachof radical A₄, is oxygen or sulfur.

The process according to the invention for preparing compounds offormula (I) is carried out in principle by methods known to thoseskilled in the art, or described for example in WO 2009/131237, WO2011/043404, WO 2011/040629, WO 2010/125985, WO 2012/086848, WO2013/018928, WO 2013/191113, WO 2013/180193 and WO 2013/180194, andinvolves reaction of a compound of formula II,

wherein Q is the radical B₁, B₂, B₃, B₄, B₅, B₆, B₇, B₈, B₉ and B₁₁,wherein R₃, R₄, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇,R₁₈, R₁₉, V₀, V₁, V₂, V₃, V₄, V₅, V₆, V₇, V₈ and L₁ are as described informula I, and the arrows in the radicals B₁-B₉ and B₁₁ show the pointof attachment to the carbonyl atom of the carboxyl group In formula II,with a compounds of formula III, IV, or V;

wherein R₁, R₂, G₁, G₂, and G₅ are as described in formula (I) and M₁ isoxygen, sulfur, or NR₃₅, in the presence of a dehydrating agent such aspolyphosphoric acid at temperature between 150° C. to 200° C., to yieldcompounds of formula Ia, Ib, and Ic, wherein the substituents are asdescribed for formula (I).

Such processes are well known and have been described for example in WO2011/040629 or WO 2009131237 (M₁ is oxygen), WO 2011088990 or Inorg.Chimica Acta, 358(9), 2701-2710; 2005 (M₁ is sulfur) and J. Am. Chem.Soc., 132(5), 1545-1557, 2010 or WO 2008128968 (M₁ is NR₃₅). The processis summarized in scheme 1 for compounds of formula Ia:

As can be seen in scheme 1, the formation of Ia occurs through theintermediacy of a compound of formula VI. It is in many casesadvantageous to thus prepare compounds of formula (I) through suchintermediates. This is illustrated for compounds of formula Ia in scheme2.

In scheme 2 compounds of formula II wherein Q is as previouslydescribed, are activated to compounds of formula IIa by methods known tothose skilled in the art and described in for example Tetrahedron, 61(46), 10827-10852, 2005. For example compounds where X₀ is halogen areformed by treatment with for example, oxallyl chloride or thionylchloride in the presence of catalytic quantities of DMF in inertsolvents such as methylene chloride or THF at temperatures between 20°C. to 100° C., preferably 25° C. Treatment of IIa with compounds offormula III, optionally in the presence of a base, e.g. trethylamine orpyridine leads to compounds of formula VI. Alternatively, compounds offormula VI can be prepared by treatment of compounds of formula II withdicyclohexyl carbodiimide (DCC) or1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) to give theactivated species IIa, wherein X₀ is X₀₁ and X₀₂ respectively, in aninert solvent, e.g. pyridine, or THF optionally in the presence of abase, e.g. triethylamine, at temperatures between 50-180° C. Compoundsof Formula VI so obtained can then be converted to compounds of formulaIa by dehydration, eg. by heating the compounds in a microwave, in thepresence of an acid catalyst, for example methane sulfonic acid, orpara-toluene sulfonic acid, in an inert solvent such as N-methylpyrollidine at temperatures between 25-180° C., preferably 130-170° C.Such processes have been described previously in WO 2010125985.Alternatively, compounds of formula VI can be converted to compounds offormula Ia (wherein M₁ is O) using triphenyl phosphine, di-isopropyl azodicarboxylate in an inert solvent such as THF at temperatures between25-50° C. Such Mitsunobu conditions have been previously described forsuch transformations (see WO2009131237). Application of such methods inthe reaction of compounds of formula II respectively IIa with compoundsof formula IV and V, leads to compounds Ib and Ic via the intermediatesVII and VIII respectively.

Alternatively, compounds of formula (I) can be prepared by reactingcompounds of formula IX, X, XI, XII, and XIII;

wherein V₀, V₁, V₂, V₃, V₄, V₅, V₆, V₇, V₈ and R₄ are as defined forformula (I) and X₀₄ is halogen, with compounds of formula III, IV and Vas described in schemes 2 and 3 to give compounds of formula XIV, XV,XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XIV, XV, XVI, XVII, andXVIII;

wherein R₁, R₂, R₄, G₁, G₂, G₅, V₀, V₁, V₂, V₃, V₄, V₅, V₆, V₇, V₃, J₁,J₂ and J₃ are as defined in formula I, M₁ is oxygen, sulfur, or NR₃₅,and X₀₄ is halogen. Compounds of formula XIV, XV, XVI, XVII, XVIII, XIX,XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, and XXVIII can be reactedwith compounds of formula XXIX

R₃—SH  (XXIX)

wherein R₃ is as described in formula I, in the presence of a suitablebase, such as alkali metal carbonates, for example sodium carbonate andpotassium carbonate or alkali metal hydrides such as sodium hydride, ina suitable solvent, at temperatures between 25-120° C. to give compoundsof formula Id, Ie, If, Ig, Ih, Ii, Ij, Ik, Il, Im, In, Io, Ip, Iq andIr:

Examples of the solvent to be used in the reaction include ethers suchas THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitrilessuch as acetonitrile. Similar chemistry has been previously described,as for example in WO 2013018928. Alternatively, the reaction can becarried out in the presence of a palladium catalyst, such astris(dibenzylideneacetone)dipalladium(0), in the presence of a phosphorligand, such as xanthphos, in an inert solvent, for example, xylene attemperatures between 100-160° C., preferably 140° C., as described byPerrio et al in Tetrahedron, 61, 5253-5259, 2005. Compounds representedby the formula (I) wherein m is 1 or 2 can be produced by oxidizing thecompounds of formula Id, Ie, If, Ig, Ih, Ii, Ij, Ik, Il, Im, In, Io, Ip,Iq and Ir. The oxidation reaction is generally conducted in the presenceof a solvent. Examples of the solvent to be used in the reaction includealiphatic halogenated hydrocarbons such-as dichloromethane andchloroform; alcohols such as methanol and ethanol; acetic acid; water;and mixtures thereof. Examples of the oxidant to be used in the reactioninclude sodium periodate and m-chloroperbenzoic acid. The amount of theoxidant to be used in the reaction is generally 1 to 3 moles, preferably1 to 1.2 moles, relative to 1 mole of the compounds Id, Ie, If, Ig, Ih,Ii, Ij, Ik, Il, Im, In, Io, Ip, Iq and Ir to produce compounds offormula (I) where m=1, and preferably 2 to 2.2 moles of oxidant,preferably metachloroperbenzoic acid, relative to 1 mole of thecompounds Id, Ie, If, Ig, Ih, Ii, Ij, Ik, Il, Im, In, Io, Ip, Iq and Irto produce compounds of formula (I) wherein m=2.

Compounds of formula I, wherein B is B₁₀, can be prepared by reacting acompound of formula XXX:

Q₁-X₀₅   (XXX),

wherein Q₁ is A₁, A₂, A₃, A₄, and A₈ and X₀₅ is a halogen or a leavinggroup OSO₂R₃₈, and the arrows in the substituents in A₁, A₂, A₃, A₄, andA₆ show the point attachment of the radical A to the substituent X₀₄,and wherein R₃₈, is C₁-C₆alkyl, C₁-C₆haloalkyl, or phenyl optionallysubstituted by nitro or C₁-C₃alkyl, with a compound of formula XXXI;

wherein, V₉, V₁₀, and V₁₁, are as described in formula I, in thepresence of a suitable base, such as sodium hydride or cesium carbonate,in an inert solvent such as dimethyl formamide, N-methylpyrollidine, oracetonitrile, at temperatures between 20-150° C., to yield compounds offormula XXXII:

Alternatively compounds of formula XXXII can be obtained by reactingcompounds of formula XXX with compounds of formula XXXI in an inertsolvent such as dioxane, in the presence of a catalytic amount of copperiodide and catalytic amount of a diamine, for exampleN,N-dimethylethylenediamine or racemictrans-N,N-dimethylcyclohexanediamine, with a base, for example potassiumcarbonate or potassium phosphate at temperatures between 50-120° C.,preferably 90-110° C. Such reactions are well precedented in theliterature and described for example in J. Org. Chem., 68, 2609-2617,2003, and Org. Letts., 9, 643-646, 2007. Compounds of formula XXXII canbe reacted with a halogenating reagent such as phosphorus oxychloride,phosphorus trichloride or tribromide, phosphorus pentachloride orpentabromide, or thionyl chloride, optionally in an inert solvent attemperatures between 25-120° C., to give compounds of formula XXXIII,wherein X_(0s) is halogen:

Compounds of formula XXXIIII can subsequently be treated with compoundsof formula XXIX;

R₃—SH  (XXIX)

wherein R₃ is as described in formula I, in the presence of a suitablebase, such as an alkaline earth metal hydride, for example sodiumhydride and a polar aprotic solvent, such as dimethyl formamide, attemperatures between 25-120° C. to give compounds of formula Is:

Oxidation of compound Is by methods known to those skilled in the art,for example using sodium periodate to prepare compounds of formula It,where m=1, or at least two equivalents of meta-chloroperbenozoic (MCPBA)in an inert solvent such as methylene chloride, leads to compounds offormula It where m=2.

The synthesis is summarized in scheme 3.

The subgroup of compounds of formula I, wherein A is A₂ and G₅ is CR₃₄,can be represented by the compounds of formula Iu

wherein Q is one of the radicals B₁, B₂, B₃, B₄, B₅, Be, B₇, B₈, B₉ orB₁₁, and R₁, R₂, G₁, G₂ and G₄ are as described in formula (I) and R₃₄is C₁-C₆alkyl or C₁-C₆haloalkyl can be prepared by reacting a compoundof formula XXXIV

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) with acompound of formula XXXV

wherein X₀₇ is a halogen or a leaving group OSO₂R₃₈ and Q is as definedabove, optionally in the presence of a suitable base in an inertsolvent.

A further process to prepare compounds of formula Iu, involves reactinga compound of formula XXXIV with a compound of XXXVa

In the presence of a Lewis acid, such as Zinc(II)iodide or Indium(III)triflate, in an inert solvent such as chlorobenzene or1,2,dichlorobenzene, with a catalytic copper(II) salt, such asCu(II)acetate, under an oxygen or air atmosphere at temperatures between100-180° C., preferably 110-140° C., to give compounds of formula Iuwherein R₃₄ is hydrogen. Such reactions have previously been describedin the literature (see Adv. Synth. Catal. 2013, 355, 1741-1747, and J.Org. Chem., 2013, 78, 12494-12504). Halogenation of compounds of formulaIu, wherein R₃₄ is hydrogen, with a halogenating agent such asN-chlorosuccinamide, N-bromosuccinamide, or N-iodosuccinamide, in apolar aprotic solvent such as acetonitrile or dimethylformamide, atambient temperature, leads to compounds of formula Iu_(c)

wherein Q, R₁, R₂, G₁, G₂ and G₄ are as described in formula (I), andX₁₅ is halogen. Compounds of formula Iu, can be reacted with compoundsR₃₄-M₀, wherein M₀ is a boronic acid, in the presence of a palladiumcatalyst to give compounds of formula Iu. When M₀ is a boronic acid, thereaction is usually carried out in the presence of a base, for examplepotassium carbonate, cesium carbonate, or potassium phosphate, in aninert solvent, such as dioxane, optionally in the presence of water,with a palladium(0) catalyst, for exampletetrakis(triphenylphosphine)palladium, at a temperature between 80-120°C. Such Suzuki reactions are well precedented in the literature, see forexample Masuda, Naoyuki et al, WO 2012133607. Compounds of formula XXXVand XXXVa can be prepared from compounds of formula II by, for example,the methods shown in scheme 4.

In scheme 4, an acyl halide of formula IIa is converted to a Weinrebamide Ib upon reaction with N, O-Dimethylhydroxylamine by methods knownto those skilled in the art and described for example in C. Ferri,“Reaktionen der Organischen Synthese”, Georg Thieme Verlag, Stuttgart,1978, page 223ff. the Weinreb amide of formula Ib is then reacted with aGrignard reagent of formula R₃₅CH₂MgHal according to the method ofWeinreb (Tetrahedron Letters 1981, 22, 3815-3818) to give compounds offormula XXXVb and XXXVa. Compounds of formula XXXVa and XXXVb can alsobe prepared by treatment of nitrile compounds of formula IIc, wherein Qis as described in formula I, with a Grignard reagent of formulaR₃₅CH₂MgHal, followed by acidic hydrolysis (as described in C. Ferri,“Reaktionen der Organischen Synthese”, Georg Thieme Verlag, Stuttgart,1978, page 223ff.).

Compounds of formula XXXVa and XXXVb can be halogenated to compounds offormula XXXV, with for example mixtures of bromine and hydrobromic acidin acetic acid (as described in Phosphorus, Sulfur and Silicon and theRelated Elements, 2013, 188(12), 1835-1844) or with, for example,copper(II)bromide in an inert solvent, for example chloroform, ethylacetate and the like, as described in J. Med. Chem., 2013, 56(1), 84-96.Alternatively compounds of formula XXXV where R₃₅ is hydrogen, can beprepared directly from compounds of formula IIa by treatment withdiazomethane or trimethyl silyl diazomethane and subsequent treatmentwith an halogen acid, for example, hydrobromic acid or hydrochloric acidin an inert solvent such as diethyl ether. Such procedures are wellknown in the literature, for example see Eu. J. Med. Chem., 1987, 22(5),457-62 and WO 2009010455.

In an analogous manner, compounds of formula Iu_(a)

wherein R₁, G₁, G₂ are as described in formula (I), and G₅ is CR₃₄ canbe prepared by reacting compounds of formula (XXXIVa),

wherein R₁, G₁, G₂, are as described in formula (I) with a compound offormula XXXV or XXXVa analogously to the preparation of compounds offormula Iu. Those skilled in the art will recognize that compounds offormula Iu_(b)

can be similarly prepared by reaction of compounds of formula XXXIVbwith compounds of formula XXXV or XXXVa, wherein G₅ is CR₃₄ as describedabove.

The subgroup of compounds of formula I, wherein A is A₂ and G₅ isnitrogen, can be represented by the compounds of formula Iv;

wherein Q is one of the radicals B₁, B₂, B₃, B₄, B₅, B₆, B₇, B₈, B₉ orB₁₁, and R₁, R₂, G₁, G₂ and G₄ are as described in formula I, can beprepared by reacting a compound of formula XXXVI;

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) and in whichX₀₀ is a halide ion or an anion of the formula —OSO₂R₃₈ with a compoundof formula IIa

wherein X₀ is a halogen and Q is as defined above, optionally in thepresence of a suitable base in an inert solvent.

Compounds of the formula XXXIV above can be prepared throughamino-dehalogenation by reacting a compound of formula XXXVII;

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) and in whichX_(0s) is a halogen or a leaving group OSO₂R₃₈, with ammonia (eithergaseous or aqueous) as a nucleophile. Ammonia may be used in equimolaramounts or in large excess in an appropriate inert solvent, optionallyin a pressurised vessel. The reaction may be performed between 0 and200° C., optionally with microwave irradiation. Ammonia equivalents suchas, for example, ammonium hydroxide NH₄OH, ammonium acetate NH₄OAc,ammonium carbonate (NH4)2CO3 may also be used as a nitrogen source.

Compounds of the formula XXXVII can be prepared by reacting a compoundof formula XXXVIII

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) with reagentssuch as, for example, phosphorus oxychloride, phosphorus trichloride ortribromide, phosphorus pentachloride or pentabromide in an inertsolvent.

Compounds of the formula XXXVIII are known in the literature. Forexample, compounds of the formula XXXVIII where G₂ is a nitrogen atomand G₁ is CR₃₁, and wherein R₁ and R₂ are as described in formula I, areknown from or can be prepared in analogy to EP1371638.

Compounds of the formula XXXVI can be prepared via N-amination byreacting a compound of formula XXXIV above withO-mesitylenesulfonylhydroxylamine (MSH) as amination reagent, asdescribed for example by Y. Tamura et al., J. Heterocyclic Chem. 1975,12, 107-110. MSH is also known in form of a precursor as itsethyl-acetohydroxamate; a pre-treatment with for example perchloric acidHClO₄ in tetrahydrofurane liberates the required amination reagent MSH.O-mesitylenesulfonyl-hydroxylamine and related aminating reagents havebeen reviewed: Y. Tamura et al., Synthesis, 1-17, 1977.

The subgroup of compounds of formula I, wherein A is A₃ and G₅ isnitrogen, can be represented by the compounds of formula Iw

wherein Q is one of the radical B₁, B₂, B₃, B₄, B₅, B₆, B₇, B₈, B₉ orB₁₁, and wherein R₁, R₂, G₁, G₂ and G₄ are as described in formula I.

When G₄ is CR₃₃ then compounds of the formula Iw can be prepared byreacting a compound of formula XXXIX

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) with acompound of formula XL

wherein X₁₀ is a halogen or a leaving group OSO₂R₃₈ and Q is as definedabove, optionally in the presence of a suitable base in an inertsolvent.

Alternatively, when G₄ is a nitrogen, compounds of the formula Iw can beprepared by reacting a compound of formula XLI

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) and in whichX₁₁ ⁻ is a halide ion or an anion of the formula ⁻OSO₂R₃₈ with acompound of formula IIa

wherein X₀ is a halogen and Q is as defined above, optionally in thepresence of a suitable base in an inert solvent.

Compounds of the formula XXXIX above can be prepared throughamino-dehalogenation by reacting a compound of formula XLII

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) and in whichX₁₂ is a halogen or a leaving group OSO₂R₃₈ with ammonia (either gaseousor aqueous) as a nucleophile. Ammonia may be used in equimolar amountsor in large excess in an appropriate inert solvent, optionally in apressurized vessel. The reaction may be performed between 0 and 200° C.,optionally with microwave irradiation. Ammonia equivalents such as, forexample, ammonium hydroxide NH₄OH, ammonium acetate NH₄OAc, and ammoniumcarbonate (NH₄)₂CO₃ may also be used as a nitrogen source.

Compounds of the formula XLII can be prepared by reacting a compound offormula XLIII

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) with reagentssuch as, for example, phosphorus oxychloride, phosphorus trichloride ortribromide, phosphorus pentachloride or pentabromide or thionyl chloridein an inert solvent.

Compounds of the formula XL can be prepared, for example, in analogy toEP1371638.

Compounds of the formula XLI can be prepared via N-amination by reactinga compound of formula XXXIX above with O-mesitylenesulfonylhydroxylamine(MSH)—or one of its equivalent—as amination reagent, as describedpreviously for the preparation of compounds of the formula XXXVI.

The subgroup of compounds of formula I, wherein A is A₇ and both G₅ andG₄ are nitrogen, can be represented by the compounds of formula Ix

wherein Q is one of the radical B₁, B₂, B₃, B₄, B₅, B₆, B₇, B₈, B₉ orB₁₁, and wherein R₁, R₂, G₁ and G₂ are as described in formula I.

Compounds of the formula Ic can be prepared by reacting a compound offormula XLIV

wherein R₁, R₂, G₁ and G₂ are as described in formula (I) with acompound of formula XLV

X₁₃-Q   (XLV),

wherein X₁₃ is a halogen or a leaving group OSO₂R₃₈ and Q is as definedabove, where the arrows in the radicals B₁, B₂, B₃, B₄, B₅, B₆, B₇, B₈,B₉ or B₁₁ show the point of attachment of the substituent X₁₃,optionally in the presence of a suitable base in an inert solvent, forexample sodium hydride in dimethylformamide, in analogy to, for example,WO10/038081.

Alternatively, compounds of the formula Ix can be prepared by reacting acompound of formula XLIV, with a compound of formula XLV underpalladium-catalyzed N-arylation conditions as described, for example, inS. L. Buchwald et al., Angew. Chem. Int. Ed., 50, 8944-8947, 2011.Compounds of the formula XLIV above can be prepared throughdiazotization by treating a compound of formula XLVI

wherein R₁, R₂, G₁ and G₂ are as described in formula I, with eithersodium nitrite and hydrohalic acid in water or with an alkyl nitrite(such as, for example, tert-butyl nitrite or isoamyl nitrite) underanhydrous conditions, optionally in presence of an acid (such as, forexample, acetic acid) in an inert solvent (such as, for example,tetrahydrofurane) at temperatures between 0 and 130° C. A typicalexample involving isoamyl nitrite and acetic acid in refluxingtetrahydrofurane may be found in I. Torrini et al., J. HeterocyclicChem., 23, 1459-1463, 1986.

Compounds of formula (I) wherein R₂₁ is C₁-C₆alykenylloxy, —C(O)R₃₆ canbe prepared as shown in scheme 5, which is illustrated for radicalA₁-B₁:

In scheme 5, compounds of formula XLVII, wherein R₁, R₂, G₁, G₂, L₁, R₃,R₄, V₁ and V₀ are as described for formula (I), and X₁₄ is halogen,preferably bromide, are reacted with compounds of formula XLVIII,wherein R₃₉ is C₁-C₅alkyl which can be mono- or polysubstituted bysubstituents selected from C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy,C₁-C₆ alkylsulphanyl, C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl,C₁-C₆haloalkylsulphinyl, C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl,C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl,C₂-C₆haloalkoxycarbonyl, cyano, hydroxy, halogen and C₃-C₆ cycloalkyl,wherein said C₃-C₆ cycloalkyl can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen andC₁-C₆alkyl, or a phenyl group which can be mono- or polysubstituted bysubstituents selected from the group consisting of C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulphanyl,C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl, C₁-C₆haloalkylsulphinyl,C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,C₁-C₆alkylamino, C₁-C₆haloalkylamino, C₂-C₈dialkylamino,C₂-C₈halodialkylamino, halogen, cyano, and nitro, in an inert solvent,such as THF, DMF, dioxane, octane, toluene, and xylene, in the presenceof a palladium catalyst, such astetrakis(triphenylphosphine)palladium(0), orBis(triphenylphosphine)palladium(II) chloride, in an inert solvent, suchas toluene, and xylene, and DMF, or a mixture of these, etc. attemperatures between 25-120° C., preferably 50-90° C. The obtainedproduct XLIX is then treated with a mineral acid, for example aqueoushydrochloric acid, in the presence of an organic co-solvent, for examplemethanol, acetone, ethanol, THF, etc. to give the product of formula 1y,where the substituents R₁, R₂, G₁, G₂, L₁, R₃, R₄, V₁, V₀ and R₃₉ are aspreviously described. Such processes are well known and have beendescribed previously in for example, Kosugi, Masanori et al, Bull. Chem.Soc. Japan, 60(2), 767-8, 1987.

Analogous chemistry can be used to introduce such a substituent in R₄,R₅, R₂₀, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, R₂₉, and R₃₀.

Compounds of formula II are in many cases commercially available, knownin the literature, or can be produced analogously to methods describedin the literature. For example3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylic acid (WO2013180194), 3-ethylsulfonylpyridine-2-carboxylic acid (WO 2013180194),3-ethylsulfonylpyrazine-2-carboxylic acid (WO 2013180194),3-ethylsulfonylthiophene-2-carboxylic acid (Synthesis, 2007, (12),1827-1832), 3-ethylsulfonyl-5-(trifluoromethyl)thiophene-2-carboxylicacid (WO 2013180193), 2-chloro-6-(trifluoromethyl)pyridine-3-carboxylicacid (WO 2013180194), 5-ethylsulfanylthiazole-4-carboxylic acid (WO2013180193) 2-ethylsulfanylthiophene-3-carboxylic acid (WO 2013180193),and 4-bromo-2-methyl-1,1-dioxo-2,3-dihydrobenzothiophene-7-carboxylicacid (WO 199909023),

In further cases, syntheses for compounds of formula II have beenespecially developed to prepare compounds of formula I and are shown inthe following schemes:

Compounds of formula III, IV, and V are commercially available, known inthe literature, or can be prepared by analogous methods to those in theliterature. For example,N-2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (WO 2012086848),6-(trifluoromethyl)pyridine-3,4-diamine (WO 2013/048214),N-3-methyl-6-(trifluoromethyl)pyridine-2,3-diamine (WO 2012/086848),N-5-methyl-2-(trifluoromethyl)pyrimidine-4,5-diamine (CAS[1023817-05-1]), N-1-methyl-4-(trifluoromethyl)benzene-1,2-diamine (WO2005065680), 3-amino-5-(trifluoromethyl)pyridin-2-ol (WO 2011049222),3-amino-5-(trifluoromethyl)-2 (1H)-Pyridinethione (WO 2011/043404). Infurther cases, syntheses for compounds of formula III, IV, and V havebeen especially developed to prepare compounds of formula I and areshown in the following schemes:

Further syntheses to compounds of formula I are illustrated in thefollowing schemes:

For preparing all further compounds of the formula (I) functionalizedaccording to the definitions of A₁-A₆ and B₁—B₁₁ there are a largenumber of suitable known standard methods, for example alkylation,halogenation, acylation, amidation, oximation, oxidation and reduction,the choice of the preparation methods which are suitable depending onthe properties (reactivity) of the substituents in the intermediates.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound of formula I can be converted in a manner known per se intoanother compound of formula I by replacing one or more substituents ofthe starting compound of formula I in the customary manner by (an)othersubstituent(s) according to the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds I, acid addition salts, for example, bytreatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties, can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomer'sthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with asuitable oxidizing agent, for example the H₂O₂/urea adduct in thepresence of an acid anhydride, e.g. trifluoroacetic anhydride. Suchoxidations are known from the literature, for example from J. Med. Chem.1989, 32, 2561 or WO 2000/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favorablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects or representatives ofthe order Acarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately oronly after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate, agood activity corresponding to a destruction rate (mortality) of atleast 50%.

The compounds of formula I can be used to combat and controlinfestations of insect pests such as Lepidoptera, Diptera, Hemiptera,Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera,Hymenoptera and Isoptera and also other invertebrate pests, for example,acarine, nematode and mollusc pests. Insects, acarines, nematodes andmolluscs are hereinafter collectively referred to as pests. The pestswhich may be combated and controlled by the use of the inventioncompounds include those pests associated with agriculture (which termincludes the growing of crops for food and fibre products), horticultureand animal husbandry, companion animals, forestry and the storage ofproducts of vegetable origin (such as fruit, grain and timber); thosepests associated with the damage of man-made structures and thetransmission of diseases of man and animals; and also nuisance pests(such as flies).

Examples of pest species which may be controlled by the compounds offormula I include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphisfabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids),Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper),Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp.(stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips),Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis(boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (whiteflies), Bemisia tabaci (white fly), Ostrinia nubilalis (European cornborer), Spodoptera littoralis (cotton leafworm), Heliothis virescens(tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpazea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pierisbrassicae (white butterfly), Plutella xylostella (diamond back moth),Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locustamigratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp.(rootworms), Panonychus ulmi (European red mite), Panonychus citri(citrus red mite), Tetranychus urticae (two-spotted spider mite),Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora(citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpusspp. (flat mites), Boophilus microplus (cattle tick), Dermacentorvariabilis (American dog tick), Ctenocephalides felis (cat flea),Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti(mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes),Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplanetaamericana (cockroach), Blatta orientalis (cockroach), termites of theMastotermitidae (for example Mastotermes spp.), the Kalotermitidae (forexample Neotermes spp.), the Rhinotermitidae (for example Coptotermesformosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R.hesperus, and R. santonensis) and the Termitidae (for exampleGlobitermes sulphureus), Solenopsis geminata (fire ant), Monomoriumpharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (bitingand sucking lice), Meloidogyne spp. (root knot nematodes), Globoderaspp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesionnematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulusspp. (citrus nematodes), Haemonchus contortus (barber pole worm),Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slug).

Further examples of the above mentioned pests are:

from the order Acarina, for example, Acalitus spp, Aculus spp,Acaricalus spp, Aceria spp, Acarus siro, Amblyomma spp., Argas spp.,Boophilus spp., Brevipalpus spp., Bryobia spp, Calipitrimerus spp.,Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp,Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp, Hyalomma spp.,Ixodes spp., Olygonychus spp, Ornithodoros spp., Polyphagotarsone latus,Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp,Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp.,Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp.and Tetranychus spp.;from the order Anoplura, for example, Haematopinus spp., Linognathusspp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;from the order Coleoptera, for example, Agriotes spp., Amphimallonmajale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylusatromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis,Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculiospp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderusabderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemushampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp.,Liogenys spp, Maecolaspis spp, Maladera castanea, Megascelis spp,Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilusspp., Otiorhynchus spp., Phyllophaga spp, Phlyctinus spp., Popilliaspp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp.,Scarabeidae, Sitophilus spp., Sitotroga spp., Somaticus spp,Sphenophorus spp, Sternechus subsignatus, Tenebrio spp., Tribolium spp.and Trogoderma spp.; from the order Diptera, for example, Aedes spp.,Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibio hortulanus,Bradysia spp, Calliphora erythrocephala, Ceratitis spp., Chrysomyiaspp., Culex spp., Cuterebra spp., Dacus spp., Delia spp, Drosophilamelanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata,Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Luciliaspp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp.,Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp,Rivelia quadrifasciata, Scatella spp, Sciara spp., Stomoxys spp.,Tabanus spp., Tannia spp. and Tipula spp.;from the order Hemiptera, for example, Acanthocoris scabrator,Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoeliathalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis,Creontiades spp, Distantiella theobroma, Dichelops furcatus, Dysdercusspp., Edessa spp, Euchistus spp., Eurydema pulchrum, Eurygaster spp.,Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp,Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoristenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp.,Piezodorus spp, Rhodnius spp., Sahlbergella singularis, Scaptocoriscastanea, Scotinophara spp; Thyanta spp, Triatoma spp., Vatiga illudens;Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscenatargionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis,Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula,Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotusspp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp,Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariellaaegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalusdictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulinaspp, Coccus hesperidum, Dalbulus maidis, Dialeurodes spp, Diaphorinacitri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum,Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphispseudobrassicae, Hyalopterus spp, Hyperomyzus pallidus, Idioscopusclypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni,Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp.,Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus,Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp.,Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter,Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigusspp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxeraspp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp.,Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica,Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphumspp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp.,Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina,Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp,Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidiascutellaris;from the order Heteroptera, for example, Cimex spp., Distantiellatheobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisaspp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,Scotinophara spp. and Triatoma spp.;from the order Homoptera, for example, Aleurothrixus floccosus,Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotusspp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosomalarigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecaniumcorni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettixspp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Planococcusspp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinariaaethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodesvaporariorum, Trioza erytreae and Unaspis citri;from the order Hymenoptera, for example, Acromyrmex, Arge spp, Attaspp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp.,Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp. and Vespa spp.;from the order Isoptera, for example, Coptotermes spp, Corniternescumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp,Microtermes spp, Reticulitermes spp.; Solenopsis geminate;from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp.,Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp.,Anticarsia gemmatalis, Archips spp., Argyresthia spp, Argyrotaenia spp.,Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadracautella, Carposina nipponensis, Chilo spp., Choristoneura spp.,Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp.,Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia,Cosmophila flava, Crambus spp, Crocidolomia binotalis, Cryptophlebialeucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis,Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina,Ephestia spp., Epinotia spp, Estigmene acrea, Etiella zinckinella,Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltiajaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellulaundalis, Herpetogramma spp, Hyphantria cunea, Keiferia lycopersicella,Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp.,Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp.,Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp, Noctuaspp, Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammenespp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophoragossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.;from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example, Blatta spp., Blattella spp.,Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtillahexadactyla, Periplaneta spp., Scapteriscus spp, and Schistocerca spp.;from the order Psocoptera, for example, Liposcelis spp.;from the order Siphonaptera, for example, Ceratophyllus spp.,Ctenocephalides spp. and Xenopsylla cheopis;from the order Thysanoptera, for example,Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp; andfrom the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the invention may also have activity against themolluscs. Examples of which include, for example, Ampullariidae; Arion(A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina;Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum);Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H.itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix(H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L.maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M.sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

The term “crops” is to be understood as including also crops that havebeen rendered tolerant to herbicides like bromoxynil or classes ofherbicides (such as, for example, HPPD inhibitors, ALS inhibitors, forexample primisulfuron, prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors) as a result of conventional methodsof breeding or genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding (mutagenesis) is Clearfield® summer rape (Canola).Examples of crops that have been rendered tolerant to herbicides orclasses of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady® and LibertyLink®.

The term “crops” is also to be understood as including also crop plantswhich have been so transformed by the use of recombinant DNA techniquesthat they are capable of synthesising one or more selectively actingtoxins, such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c),CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, orvegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsine inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2),CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidalproteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly alsohybrid toxins, truncated toxins and modified toxins. Hybrid toxins areproduced recombinantly by a new combination of different domains ofthose proteins (see, for example, WO 02/15701). Truncated toxins, forexample a truncated CryIA(b), are known. In the case of modified toxins,one or more amino acids of the naturally occurring toxin are replaced.In such amino acid replacements, preferably non-naturally presentprotease recognition sequences are inserted into the toxin, such as, forexample, in the case of CryIIIA055, a cathepsin-D-recognition sequenceis inserted into a CryIIIA toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. CryI-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGardRootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGardPlus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin);Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I®(maize variety that expresses a CryIF(a2) toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a CryIA(c) toxin); Bollgard I® (cotton variety that expressesa CryIA(c) toxin); Bollgard 1® (cotton variety that expresses a CryIA(c)and a CryIIA(b) toxin); VIPCOT® (cotton variety that expresses a VIPtoxin); NewLeaf® (potato variety that expresses a CryIIIA toxin);NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated CryIA(b) toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a CryIA(b) toxin. Bt176 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCryIIIA toxin. This toxin is Cry3A055 modified by insertion of acathepsin-D-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a CryIIIB(b1) toxin and has resistance to certain Coleopterainsects.5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a CryIA(b) toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Crops may also be modified for enhanced resistance to fungal (forexample Fusarium, Anthracnose, or Phytophthora), bacterial (for examplePseudomonas) or viral (for example potato leafroll virus, tomato spottedwilt virus, cucumber mosaic virus) pathogens.

Crops also include those that have enhanced resistance to nematodes,such as the soybean cyst nematode.

Crops that are tolerance to abiotic stress include those that haveenhanced tolerance to drought, high salt, high temperature, chill,frost, or light radiation, for example through expression of NF-YB orother proteins known in the art.

Crops that exhibit enhanced yield or quality include those with improvedflowering or fruit ripening properties (such as delayed ripening);modified oil, starch, amino acid, fatty acid, vitamin, phenolic or othercontent (such as Vistive™ soybean variety); enhanced nutrientutilisation (such as improved nitrogen assimilation); and enhancedquality plant product (such as higher quality cotton fibre).

Further areas of use of the compounds and compositions according to theinvention are the protection of stored goods and storerooms and theprotection of raw materials, such as wood, textiles, floor coverings orbuildings, and also in the hygiene sector, especially the protection ofhumans, domestic animals and productive livestock against pests of thementioned type.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents.

In one embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 2003/034823, U.S. Pat. No. 5,631,072, WO 2005/64072,WO2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesAA and BB:

TABLE AA Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE BB Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain- mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain- ash Pseudopityophthorus pruinosus Oak, American beech, Blackcherry, Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam, HophornbeamSesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

In the hygiene sector, the compounds and compositions according to theinvention are active against ectoparasites such as hard ticks, softticks, mange mites, harvest mites, flies (biting and licking), parasiticfly larvae, lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorusspp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compounds and compositions according to the invention are alsosuitable for protecting against insect infestation in the case ofmaterials such as wood, textiles, plastics, adhesives, glues, paints,paper and card, leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The present invention therefore provides an insecticidal, acaricidal,nematicidal or molluscicidal composition, preferably an insecticidal oracaricidal composition comprising an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compound offormula I and a suitable carrier or diluent therefor.

In a further aspect the invention provides a method of combating andcontrolling pests which comprises applying an insecticidally,acaricidally, nematicidally or molluscicidally effective amount,preferably an insecticidally and acaricidally effective amount of acompound of formula I or a composition comprising a compound of formulaI, to a pest, a locus of pest, or to a plant susceptible to attack by apest, with the exception of a method for treatment of the human oranimal body by surgery or therapy and diagnostic methods practised onthe human or animal body.

The compounds of formula I are preferably used against insects oracarines.

The term “plant” as used herein includes seedlings, bushes and trees.

The invention also relates to a pesticidal composition, which, inaddition to comprising the compound of formula I, comprises formulationadjuvants.

The invention therefore also relates to pesticidal compositions such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, solublepowders, dispersible powders, wettable powders, dusts, granules orencapsulations in polymeric substances, which comprise—at least—one ofthe active ingredients according to the invention and which are to beselected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, asolid active ingredient for example in a specific particle size, or,preferably, together with—at least—one of the auxiliaries conventionallyused in the art of formulation, such as extenders, for example solventsor solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partiallyhydrogenated aromatic hydrocarbons, preferably the fractions C8 to C12of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols such as ethanol, propanol or butanol,glycols and their ethers and esters such as propylene glycol,dipropylene glycol ether, ethylene glycol or ethylene glycol monomethylether or ethylene glycol monoethyl ether, ketones, such ascyclohexanone, isophorone or diacetone alcohol, strongly polar solvents,such as N-methylpyrrolid-2-one, dimethyl sulfoxide orN,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils,such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil,and silicone oils.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly disperse silicas or highlydisperse absorbtive polymers. Suitable particulate adsorptive carriersfor granules are porous types, such as pumice, brick grit, sepiolite orbentonite, and suitable non-sorptive carrier materials are calcite orsand. In addition, a large number of granulated materials of inorganicor organic nature can be used, in particular dolomite or comminutedplant residues.

Suitable surface-active compounds are, depending on the type of theactive ingredient to be formulated, non-ionic, cationic and/or anionicsurfactants or surfactant mixtures which have good emulsifying,dispersing and wetting properties. The surfactants mentioned below areonly to be considered as examples; a large number of further surfactantswhich are conventionally used in the art of formulation and suitableaccording to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids or of alkyl phenols which may containapproximately 3 to approximately 30 glycol ether groups andapproximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatichydrocarbon radical or approximately 6 to approximately 18 carbon atomsin the alkyl moiety of the alkyl phenols. Also suitable arewater-soluble polyethylene oxide adducts with polypropylene glycol,ethylenediaminopo¬lypropylene glycol or alkyl polypropylene glycolhaving 1 to approximately 10 carbon atoms in the alkyl chain andapproximately 20 to approximately 250 ethylene glycol ether groups andapproximately 10 to approximately 100 propylene glycol ether groups.Normally, the abovementioned compounds contain 1 to approximately 5ethylene glycol units per propy¬lene glycol unit. Examples which may bementioned are nonylphenoxypolyethoxyethanol, castor oil polyglycolether, polypropylene glycol/polyethylene oxide adducts,tributylpheno¬xypolyethoxyethanol, polyethylene glycol oroctylphenoxypolyethoxyethanol. Also suitable are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium saltswhich generally have at least one alkyl radical of approximately 8 toapproximately 22 C atoms as substituents and as further substituents(unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzylradicals. The salts are preferably in the form of halides,methylsulfates or ethylsulfates. Examples are stearyltrimethylammoniumchloride and benzylbis(2-chloroethyl)ethyl¬ammonium bromide. Examples ofsuitable anionic surfactants are water-soluble soaps or water-solublesynthetic surface-active compounds. Examples of suitable soaps are thealkali, alkaline earth or (unsubstituted or substituted) ammonium saltsof fatty acids having approximately 10 to approximately 22 C atoms, suchas the sodium or potassium salts of oleic or stearic acid, or of naturalfatty acid mixtures which are obtainable for example from coconut ortall oil; mention must also be made of the fatty acid methyl taurates.However, synthetic surfactants are used more frequently, in particularfatty sulfonates, fatty sulfates, sulfonated benzimidazole derivativesor alkylaryl sulfonates. As a rule, the fatty sulfonates and fattysulfates are present as alkali, alkaline earth or (substituted orunsubstituted) ammonium salts and they generally have an alkyl radicalof approximately 8 to approximately 22 C atoms, alkyl also to beunderstood as including the alkyl moiety of acyl radicals; exampleswhich may be mentioned are the sodium or calcium salts of lignosulfonicacid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixtureprepared from natural fatty acids. This group also includes the salts ofthe sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxideadducts. The sulfonated benzimidazole derivatives preferably contain 2sulfonyl groups and a fatty acid radical of approximately 8 toapproximately 22 C atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolammonium salts of decylbenzenesulfonicacid, of dibutyl¬naphthalenesulfonic acid or of a naphthalenesulfonicacid/formaldehyde condensate. Also possible are, furthermore, suitablephosphates, such as salts of the phosphoric ester of ap-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids. Furthersuitable phosphates are tris-esters of phosphoric acid with aliphatic oraromatic alcohols and/or bis-esters of alkyl phosphonic acids withaliphatic or aromatic alcohols, which are a high performance oil-typeadjuvant. These tris-esters have been described, for example, in WO01/47356, WO 00/56146, EP-A-0579052 or EP-A-1018299 or are commerciallyavailable under their chemical name. Preferred tris-esters of phosphoricacid for use in the new compositions are tris-(2-ethylhexyl) phosphate,tris-n-octyl phosphate and tris-butoxyethyl phosphate, wheretris-(2-ethylhexyl) phosphate is most preferred. Suitable bis-ester ofalkyl phosphonic acids arebis-(2-ethylhexyl)-(2-ethylhexyl)-phosphonate,bis-(2-ethylhexyl)-(n-octyl)-phosphonate, dibutyl-butyl phosphonate andbis(2-ethylhexyl)-tripropylene-phosphonate, wherebis-(2-ethylhexyl)-(n-octyl)-phosphonate is particularly preferred.

The compositions according to the invention can preferably additionallyinclude an additive comprising an oil of vegetable or animal origin, amineral oil, alkyl esters of such oils or mixtures of such oils and oilderivatives. The amount of oil additive used in the compositionaccording to the invention is generally from 0.01 to 10%, based on thespray mixture. For example, the oil additive can be added to the spraytank in the desired concentration after the spray mixture has beenprepared. Preferred oil additives comprise mineral oils or an oil ofvegetable origin, for example rapeseed oil such as ADIGOR® and MERO®,olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO®(Rhône-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin,for example the methyl derivatives, or an oil of animal origin, such asfish oil or beef tallow. A preferred additive contains, for example, asactive components essentially 80% by weight alkyl esters of fish oilsand 15% by weight methylated rapeseed oil, and also 5% by weight ofcustomary emulsifiers and pH modifiers. Especially preferred oiladditives comprise alkyl esters of C₈-C₂₂ fatty acids, especially themethyl derivatives of C₁₂-C₁₈ fatty acids, for example the methyl estersof lauric acid, palmitic acid and oleic acid, being important. Thoseesters are known as methyl laurate (CAS-111-82-0), methyl palmitate(CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acidmethyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those andother oil derivatives are also known from the Compendium of HerbicideAdjuvants, 5th Edition, Southern Illinois University, 2000. Also,alkoxylated fatty acids can be used as additives in the inventivecompositions as well as polymethylsiloxane based additives, which havebeen described in WO 2008/037373.

The application and action of the oil additives can be further improvedby combining them with surface-active substances, such as non-ionic,anionic or cationic surfactants. Examples of suitable anionic, non-ionicand cationic surfactants are listed on pages 7 and 8 of WO 97/34485.Preferred surface-active substances are anionic surfactants of thedodecylbenzylsulfonate type, especially the calcium salts thereof, andalso non-ionic surfactants of the fatty alcohol ethoxylate type. Specialpreference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having adegree of ethoxylation of from 5 to 40. Examples of commerciallyavailable surfactants are the Genapol types (Clariant AG). Alsopreferred are silicone surfactants, especially polyalkyl-oxide-modifiedheptamethyltrisiloxanes, which are commercially available e.g. as SilwetL-77®, and also perfluorinated surfactants. The concentration ofsurface-active substances in relation to the total additive is generallyfrom 1 to 30% by weight. Examples of oil additives that consist ofmixtures of oils or mineral oils or derivatives thereof with surfactantsare Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP OilUK Limited, GB).

The said surface-active substances may also be used in the formulationsalone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oiladditive/surfactant mixture can contribute to a further enhancement ofaction. Suitable solvents are, for example, Solvesso® (ESSO) andAromatic Solvent® (Exxon Corporation). The concentration of suchsolvents can be from 10 to 80% by weight of the total weight. Such oiladditives, which may be in admixture with solvents, are described, forexample, in U.S. Pat. No. 4,834,908. A commercially available oiladditive disclosed therein is known by the name MERGE® (BASFCorporation). A further oil additive that is preferred according to theinvention is SCORE® (Syngenta Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance theactivity of the compositions according to the invention it is alsopossible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to beadded to the spray mixture. Formulations of synthetic latices, such as,for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene(e.g. Bond®, Courier® or Emerald®) can also be used. Solutions thatcontain propionic acid, for example Eurogkem Pen-e-trate®, can also bemixed into the spray mixture as activity-enhancing agents.

The term “active ingredient” refers to one of the compounds of formulaI, especially the compounds of formula I specifically disclosed in thetables. It also refers to mixtures of the compound of formula I, inparticular a compound selected from said Table 1, with otherinsecticides, fungicides, herbicides, safeners, adjuvants and the like,which mixtures are specifically disclosed below.

The compositions can also comprise further solid or liquid auxiliaries,such as stabilizers, for example unepoxidized or epoxidized vegetableoils (for example epoxidized coconut oil, rapeseed oil or soya oil),antifoams, for example silicone oil, preservatives, viscosityregulators, binders and/or tackifiers; fertilizers, in particularnitrogen containing fertilizers such as ammonium nitrates and urea asdescribed in WO 2008/017388, which can enhance the efficacy of theinventive compounds; or other active ingredients for achieving specificeffects, for example ammonium or phosphonium salts, in particularhalides, (hydrogen)sulphates, nitrates, (hydrogen)carbonates, citrates,tartrates, formiates and acetates, as described in WO 2007/068427 and WO2007/068428, which also can enhance the efficacy of the inventivecompounds and which can be used in combination with penetrationenhancers such as alkoxalated fatty acids; bactericides, fungicides,nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compositions according to the invention are also suitable for theprotection of plant propagation material, for example seeds, such asfruit, tubers or kernels, or nursery plants, against pests of theabovementioned type. The propagation material can be treated with thecompositions prior to planting, for example seed can be treated prior tosowing. Alternatively, the compositions can be applied to seed kernels(coating), either by soaking the kernels in a liquid composition or byapplying a layer of a solid composition. It is also possible to applythe compositions when the propagation material is planted to the site ofapplication, for example into the seed furrow during drilling. Thesetreatment methods for plant propagation material and the plantpropagation material comprising a compound of formula (I) as definedabove are further subjects of the invention.

Further methods of application of the compositions according to theinvention comprise drip application onto the soil, dipping of parts ofplants such as roots bulbs or tubers, drenching the soil, as well assoil injection. These methods are known in the art.

In order to apply a compound of formula I as an insecticide, acaricide,nematicide or molluscicide to a pest, a locus of pest, or to a plantsusceptible to attack by a pest, a compound of formula I is usuallyformulated into a composition which includes, in addition to thecompound of formula I, a suitable inert diluent or carrier and,optionally, a formulation adjuvant in form of a surface active agent(SFA) as described herein or, for example, in EP-B-1062217. SFAs arechemicals which are able to modify the properties of an interface (forexample, liquid/solid, liquid/air or liquid/liquid interfaces) bylowering the interfacial tension and thereby leading to changes in otherproperties (for example dispersion, emulsification and wetting).

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%,of active ingredient of the formula I and 1 to 99.9%, especially 5 to99.9%, of at least one solid or liquid adjuvant, it being possible as arule for 0 to 25%, especially 0.1 to 20%, of the composition to besurfactants (% in each case meaning percent by weight). Whereasconcentrated compositions tend to be preferred for commercial goods, theend consumer as a rule uses dilute compositions which have substantiallylower concentrations of active ingredient.

Typical rates of concentration are between 0.1 and 1000 ppm, preferablybetween 0.1 and 500 ppm, of active ingredient. The rate of applicationper hectare is generally 1 to 2000 g of active ingredient per hectare,in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

When used in a seed dressing, a compound of formula I is used at a rateof 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably 0.005 gto 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

Preferred seed treatment pre-mix formulations are aqueous suspensionconcentrates. The formulation can be applied to the seeds usingconventional treating techniques and machines, such as fluidized bedtechniques, the roller mill method, rotostatic seed treaters, and drumcoaters. Other methods, such as spouted beds may also be useful. Theseeds may be presized before coating. After coating, the seeds aretypically dried and then transferred to a sizing machine for sizing.Such procedures are known in the art.

The compositions can be chosen from a number of formulation types,including dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), oil-based suspension concentrate (OD), aerosols,fogging/smoke formulations, capsule suspensions (CS) and seed treatmentformulations. The formulation type chosen in any instance will dependupon the particular purpose en-visaged and the physical, chemical andbiological properties of the compound of formula I.

Dustable powders (DP) may be prepared by mixing a compound of formula Iwith one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulphur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula Iwith one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulphate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula Iwith one or more solid diluents or carriers, one or more wetting agentsand, preferably, one or more dispersing agents and, optionally, one ormore suspending agents to facilitate the dispersion in liquids. Themixture is then ground to a fine powder. Similar compositions may alsobe granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of acompound of formula I and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound offormula I (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of formula I (or a solution thereof, in a suitable agent) on toa hard core material (such as sands, silicates, mineral carbonates,sulphates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof formula I in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallisation in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of formula I in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),

N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment. Preparation ofan EW involves obtaining a compound of formula I either as a liquid (ifit is not a liquid at room temperature, it may be melted at a reasonabletemperature, typically below 70° C.) or in solution (by dissolving it inan appropriate solvent) and then emulsifiying the resultant liquid orsolution into water containing one or more SFAs, under high shear, toproduce an emulsion. Suitable solvents for use in EWs include vegetableoils, chlorinated hydrocarbons (such as chlorobenzenes), aromaticsolvents (such as alkylbenzenes or alkylnaphthalenes) and otherappropriate organic solvents which have a low solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound offormula I is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in in ECs or in EWs. An ME may be either anoil-in-water or a water-in-oil system (which system is present may bedetermined by conductivity measurements) and may be suitable for mixingwater-soluble and oil-soluble pesticides in the same formulation. An MEis suitable for dilution into water, either remaining as a microemulsionor forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound offormula I. SCs may be prepared by ball or bead milling the solidcompound of formula I in a suitable medium, optionally with one or moredispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of formula I may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Oil-based suspension concentrate (OD) may be prepared similarly bysuspending finely divided insoluble solid particles of a compound offormula I in an organic fluid (for example at least one mineral oil orvegetable oil). ODs may further comprise at least one penetrationpromoter (for example an alcohol ethoxylate or a related compound), atleast one non-ionic surfactants and/or at least one anionic surfactant,and optionally at least one additive from the group of emulsifiers,foam-inhibiting agents, preservatives, anti-oxidants, dyestuffs, and/orinert filler materials. An OD is intended and suitable for dilution withwater before use to produce a spray solution with sufficient stabilityto allow spray application through appropriate equipment.

Aerosol formulations comprise a compound of formula I and a suitablepropellant (for example n-butane). A compound of formula I may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurised, hand-actuated spray pumps.

A compound of formula I may be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating, in an enclosedspace, a smoke containing said compound. Capsule suspensions (CS) may beprepared in a manner similar to the preparation of EW formulations butwith an additional polymerisation stage such that an aqueous dispersionof oil droplets is obtained, in which each oil droplet is encapsulatedby a polymeric shell and contains a compound of formula I and,optionally, a carrier or diluent therefor. The polymeric shell may beproduced by either an interfacial polycondensation reaction or by acoacervation procedure. The compositions may provide for controlledrelease of the compound of formula I and they may be used for seedtreatment. A compound of formula I may also be formulated in abiodegradable polymeric matrix to provide a slow, controlled release ofthe compound.

A compound of formula I may also be formulated for use as a seedtreatment, for example as a powder composition, including a powder fordry seed treatment (DS), a water soluble powder (SS) or a waterdispersible powder for slurry treatment (WS), or as a liquidcomposition, including a flowable concentrate (FS), a solution (LS) or acapsule suspension (CS). The preparations of DS, SS, WS, FS and LScompositions are very similar to those of, respectively, DP, SP, WP, SC,OD and DC compositions described above. Compositions for treating seedmay include an agent for assisting the adhesion of the composition tothe seed (for example a mineral oil or a film-forming barrier).

A composition of the present invention may include one or more additivesto improve the biological performance of the composition (for example byimproving wetting, retention or distribution on surfaces; resistance torain on treated surfaces; or uptake or mobility of a compound of formulaI). Such additives include surface active agents (SFAs), spray additivesbased on oils, for example certain mineral oils, vegetable oils ornatural plant oils (such as soy bean and rape seed oil), and blends ofthese with other bio-enhancing adjuvants (ingredients which may aid ormodify the action of a compound of formula I). Increasing the effect ofa compound of formula I may for example be achieved by adding ammoniumand/or phosphonium salts, and/or optionally at least one penetrationpromotor such as fatty alcohol alkoxylates (for example rape oil methylester) or vegetable oil esters.

Wetting agents, dispersing agents and emulsifying agents may be surfaceactive agents (SFAs) of the cationic, anionic, amphoteric or non-ionictype.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), salts of sulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, calcium dodecylbenzenesulphonate,butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ethersulphates (for example sodium laureth-3-sulphate), ether carboxylates(for example sodium laureth-3-carboxylate), phosphate esters (productsfrom the reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulphosuccinamates, paraffin or olefine sulphonates, taurates andlignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

A compound of formula I may be applied by any of the known means ofapplying pesticidal compounds. For example, it may be applied,formulated or unformulated, to the pests or to a locus of the pests(such as a habitat of the pests, or a growing plant liable toinfestation by the pests) or to any part of the plant, including thefoliage, stems, branches or roots, to the seed before it is planted orto other media in which plants are growing or are to be planted (such assoil surrounding the roots, the soil generally, paddy water orhydroponic culture systems), directly or it may be sprayed on, dustedon, applied by dipping, applied as a cream or paste formulation, appliedas a vapour or applied through distribution or incorporation of acomposition (such as a granular composition or a composition packed in awater-soluble bag) in soil or an aqueous environment.

A compound of formula I may also be injected into plants or sprayed ontovegetation using electrodynamic spraying techniques or other low volumemethods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions ordispersions) are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient, the concentratebeing added to water before use. These concentrates, which may includeDCs, SCs, ODs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are oftenrequired to withstand storage for prolonged periods and, after suchstorage, to be capable of addition to water to form aqueous preparationswhich remain homogeneous for a sufficient time to enable them to beapplied by conventional spray equipment. Such aqueous preparations maycontain varying amounts of a compound of formula I (for example 0.0001to 10%, by weight) depending upon the purpose for which they are to beused.

A compound of formula I may be used in mixtures with fertilisers (forexample nitrogen-, potassium- or phosphorus-containing fertilisers, andmore particularly ammonium nitrate and/or urea fertilizers). Suitableformulation types include granules of fertiliser. The mixtures suitablycontain up to 25% by weight of the compound of formula I.

Preferred compositions are composed in particular as follows (%=percentby weight):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 5 to 20%surfactant: 1 to 30%, preferably 10 to 20%solvent: 5 to 98%, preferably 70 to 85%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1%solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%water: 94 to 24%, preferably 88 to 30%surfactant: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%surfactant: 0.5 to 20%, preferably 1 to 15%solid carrier: 5 to 99%, preferably 15 to 98%

Granulates:

active ingredient: 0.5 to 30%, preferably 3 to 15%solid carrier: 99.5 to 70%, preferably 97 to 85%

PREPARATORY EXAMPLES

“Mpt.” means melting point in ° C. Free radicals represent methylgroups.

LCMS Methods: Method (SQD13)

Spectra were recorded on a Mass Spectrometer from Waters (SQD Singlequadrupole mass spectrometer) equipped with an electrospray source(Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range:30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment and diode-array detector. Solventdegasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 □m, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

Method (ZCQ 13):

Spectra were recorded on a Mass Spectrometer from Waters (ZQ Singlequadrupole mass spectrometer) equipped with an electrospray source(Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range:30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment and diode-array detector. Solventdegasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 □m, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min0% B, 100% A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.

Method (ZDQ 13):

Spectra were recorded on a Mass Spectrometer from Waters (ZQ Singlequadrupole mass spectrometer) equipped with an electrospray source(Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range:30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment and diode-array detector. Solventdegasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 □m, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

Method (ZQ2000):

ZQ2000 Mass Spectrometer from Waters (Single quadrupole massspectrometer)

Ionisation method: Electrospray

Polarity: positive ions

Capillary (kV) 3.5, Cone (V) 60.00, Extractor (V) 3.00, SourceTemperature (° C.) 150, Desolvation Temperature (° C.) 350, Cone GasFlow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 800

Mass range: 140 to 800 Da

DAD Wavelength range (nm): 210 to 400

Method Waters ACQUITY UPLC with the following HPLC gradient conditions(Solvent A: Water/Methanol 9:1, 0.1% formic acid and Solvent B:Acetonitrile, 0.1% formic acid)

Time (minutes) A (%) B (%) Flow rate (ml/min) 0 100 0 0.75 2.5 0 1000.75 2.8 0 100 0.75 3.0 100 0 0.75

Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm;Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron;Temperature: 60° C.

¹H and ¹⁹F NMR Measurements: Measured on a Brucker 400 MHz or 300 MHzspectrometer, chemical shifts given in ppm relevant to a TMS standard.Spectra measured in solvents indicated.

Mass Spectroscopy Method MS

LC-20AD Mass Spectrometer from Shimadzu (Single quadrupole massspectrometer)

Instrument Parameters:

Ionisation method: ElectrosprayPolarity: positive and negative ions

Capillary (kV) 1.50

Cone (V) unknown

Extractor (V) 5.00 Source Temperature (° C.) 200 Desolvation Temperature(° C.) 250 Cone gas Flow (I/Hr) 90 Desolvation gas Flow (I/Hr) 90

Mass range: 50 to 1000 Da

Example P1:2-methyl-7-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-4-(trifluoromethyl)-2,3-dihydrobenzothiophene1,1-dioxide (Compound A1.014-B2.022)

Step A:2-methyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-4-(trifluoromethyl)-2,3-dihydrobenzothiophene-7-carboxamide

A suspension of2-methyl-1,1-dioxo-4-(trifluoromethyl)-2,3-dihydrobenzothiophene-7-carboxylicacid (308 mg, 1.05 mmol, prepared as described in WO 9909023) andN2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (200 mg 1.05 mmol,prepared as described in WO 2012/092051) in THF (15 ml) was treated3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine (487 mg, 3.14mmol) and pyridine (100 mg, 1.26 mmol). The reaction mixture was stirredfor 18 hours and then diluted with ethyl acetate and 1N HCl. The organicphase was separated and the aqueous phase extracted with ethyl acetate.The combined organic phases were washed with water, dried over anhydrousNa₂SO₄, filtered and concentrated in vacuo. Purification by flashchromatography eluting with ethyl acetate:cyclohexane 1:1, gave thetitle product (105 mg, 21%) as a white solid. LCMS (method SQD13): 468(M+H), retention time 0.97 min.

Step B:2-methyl-7-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-4-(trifluoromethyl)-2,3-dihydrobenzothiophene1,1-dioxide (Compound A1.014-B2.022)

A solution of2-methyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-4-(trifluoromethyl)-2,3-dihydrobenzothiophene-7-carboxamide(71 mg, 0.15 mmol) and toluene-4-sulphonic acid (8 mg, 0.05 mmol)dissolved in 1-methylpyrrolidin-2-one (1 ml) was heated at 160° C. for100 min in the microwave. After this time, the reaction mixture was ispoured into water, extracted with ethyl acetate, dried over anhydrousNa₂SO₄, filtered and concentrated in vacuo. The product obtained wastriturated with cyclohexane to give the title compound (45 mg, 66%, as awhite solid with mpt. 206° C. LCMS (method SQD13): 450 (M+H), retentiontime 0.99 min.

¹H NMR (400 MHz, CDCl₃) d ppm 8.77 (d, J=1.5 Hz, 1H); 8.42 (d, J=1.5 Hz,1H); 8.05 (d, J=8.1 Hz, 1H); 7.75 (d, J=7.1 Hz, 1H); 3.90 (s, 3H); 3.74(d, J=16.9, 8.1 Hz, 1H) 3.52-3.68 (m, 1H) 3.19 (dd, J=16.87, 8.1 Hz,1H); 1.55 ppm (d, J=7.0 Hz, 3H).

Example P2:4-bromo-2-methyl-7-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-2,3-dihydrobenzothiophene1,1-dioxide (Compound A1.014-B2.023)

Step A:4-bromo-2-methyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-2,3-dihydrobenzothiophene-7-carboxamide

A solution of4-bromo-2-methyl-1,1-dioxo-2,3-dihydrobenzothiophene-7-carboxylic acid(320 mg, 1 mmol, prepared as described in WO 9909023) in dichloromethane(10 ml) was treated with oxallyl chloride (170 mg, 1.3 mmol) and 1-2drops of DMF at room temperature. After 1 hr,N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (200 mg, 1.0 mmol),and triethylamine (100 mg, 1.2 mmol) and were added and the reactionmixture stirred at room temperature until reaction completion. Thereaction mixture was diluted with methylene chloride, washed with water,dried over anhydrous Na₂SO₄, filtered and concentrated in vacuo.Purification by flash chromatography eluting with ethylacetate:cyclohexane 1:1 to give the title compound (240 mg, 48%) as ayellow solid. LCMS (method SQD13): 478/480 (M+H), retention time 0.95min.

Step B:4-bromo-2-methyl-7-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-2,3-dihydrobenzothiophene1,1-dioxide (A1.014-B2.023)

A solution of4-bromo-2-methyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-2,3-dihydrobenzothiophene-7-carboxamide(210 mg, 0.44 mmol) and toluene-4-sulphonic acid (23 mg, 0.13 mmol)dissolved in 1-methylpyrrolidin-2-one (3 ml) was heated at 160° C. for 1hr in the microwave. After this time, the reaction mixture was is pouredinto water, extracted with ethyl acetate, dried over anhydrous Na₂SO₄,filtered and concentrated in vacuo. Purification by flash chromatographyeluting with ethyl acetate:cyclohexane (0/100)->(50/50, gave the titlecompound as white crystals. LCMS (method SQD13): 460/462 (M+H),retention time 0.97 min.

¹H NMR (400 MHz, CDCl₃) d ppm 8.76 (d, J=1.10 Hz, 1H); 8.41 (d, J=1.1Hz, 1H); 8.22 (d, J=7.70 Hz, 1H); 7.73 (d, J=7.70 Hz, 1H); 4.02 (dd,J=17.8, 7.5 Hz, 1H); 3.44-3.60 (m, 1H); 3.35 (dd, J=17.8, 7.5 Hz, 1H);2.74 (s, 3H) 1.51 ppm (d, J=7.0 Hz, 3H).

Example P3: 2-[4-ethylsulfonyl-6-(trifluoromethyl)pyridazin-3-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine(A1.014-B1.058)

Step A: 5-ethylsulfanyl-3-(trifluoromethyl)-1H-pyridazin-6-one

EtSNa (100 mg, 1.2 mmol) was added to a solution of5-bromo-3-(trifluoromethyl)-1H-pyridazin-6-one (243 mg, 1 mmol, Preparedas described in WO 2008128995) in 10 ml of DMF. After the addition, themixture was stirred at room temperature for 2 hours. Then the mixturewas poured into water and extracted with ethyl acetate three times. Thecombined organic layers were dried over sodium sulfate, filtered andconcentrated under reduced pressure. The residue was purified by columnchromatography on silica gel to give5-ethylsulfanyl-3-(trifluoromethyl)-1H-pyridazin-6-one (182 mg, 81%). ¹HNMR (300 Mz, DMSO-d₆): δ: 1.27 (t, 3H), 3.00 (q, 2H), 7.38 (s, 1H),13.63 (s, 1H); ¹⁹F NMR (400 MHz, DMSO-d₆): δ−65.49 (s, 3F); ESI-MS: 223(M−H)⁻.

Step B: 3-chloro-4-ethylsulfanyl-6-(trifluoromethyl)Pyridazine

A mixture of 5-ethylsulfanyl-3-(trifluoromethyl)-1H-pyridazin-6-one (5.8g, 26 mmol) in 25 ml of POCl₃ was refluxed for 16 h. Then, the reactionmixture was cooled to room temperature and POCl₃ was distilled off underreduced pressure. The residue was poured into water and adjusted toalkaline with sodium hydroxide. The resulting mixture was extracted withethyl acetate three times. The combined organic layers were dried oversodium sulfate, filtered and concentrated under reduced pressure. Thecrude product was purified by column chromatography on silica gel togive 3-chloro-4-ethylsulfanyl-6-(trifluoromethyl)pyridazine (4.9 g,79%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.31 (t, 3H), 3.23 (q, 2H), 8.00 (s,1H); ¹F NMR (300 Mz, DMSO-d₆): δ−65.19 (s, 3F); ESI-MS(+): 243 (M+H)⁺.

Step C: methyl4-ethylsulfanyl-6-(trifluoromethyl)pyridazine-3-carboxylate

Carbon monoxide gas was introduced to a mixture of3-chloro-4-ethylsulfanyl-6-(trifluoromethyl)pyridazine (2.5 g, 10 mmol),Pd(OAc)₂ (232 mg, 0.1 mmol), dppf (572 mg, 0.1 mmol) and Et₃N (3.1 g, 30mmol) in 30 ml of MeOH, and the internal pressure was increased to 1.5MPa. Then, the reaction was stirred at 80° C. for 16 h. The reactionmixture was cooled to room temperature and concentrated under reducedpressure. The residue was purified by column chromatography on silicagel to give methyl4-ethylsulfanyl-6-(trifluoromethyl)pyridazine-3-carboxylate (1.0 g,37%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.28 (t, 3H), 3.19 (q, 2H), 3.99 (s,3H), 8.01 (s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−65.61 (s, 3F);ESI-MS(+): 267(M+H)⁺, 289 (M+Na)⁺.

Step D: 4-ethylsulfanyl-6-(trifluoromethyl)pyridazine-3-carboxylic acid

A mixture of methyl4-ethylsulfanyl-6-(trifluoromethyl)pyridazine-3-carboxylate (532 mg, 2mmol) and LiOH (96 mg, 4 mmol) in 30 ml of THF and 6 ml of H₂O wasstirred at room temperature for 30 min. Then the mixture was poured intowater and adjusted PH to 3˜4 with diluted hydrochloric acid. Theresulting mixture was extracted with ethyl acetate three times. Thecombined organic layers were dried over sodium sulfate, filtered andconcentrated under reduced pressure to afford4-ethylsulfanyl-6-(trifluoromethyl)pyridazine-3-carboxylic acid (398 mg,79%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.22 (t, 3H), 3.16 (q, 2H), 8.03 (s,1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−65.52 (s, 3F); ESI-MS(−): 267(M−H)⁻.

Step E:4-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-6-(trifluoromethyl)pyridazine-3-carboxamide

A mixture 4-ethylsulfanyl-6-(trifluoromethyl)pyridazine-3-carboxylicacid (230 mg, 0.9 mmol),N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (209 mg, 1.1 mmol,prepared as described in WO 2012092051), HATU (520 mg, 1.4 mmol), DIPEA(235 mg, 1.8 mmol) in 20 ml of DMF was stirred at room temperature for16 h. Then the mixture was poured into water and extracted with ethylacetate three times. The combined organic layers were dried over sodiumsulfate, filtered and concentrated in vacuo. The residue was purified bycolumn chromatography on silica gel to give4-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-6-(trifluoromethyl)pyridazine-3-carboxamide(369 mg, 95%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.30 (t, 3H), 2.87 (d, 3H),3.12 (q, 2H), 7.03 (s, 1H), 7.77 (s, 1H), 8.07 (s, 1H), 8.33 (s, 1H),10.54 (s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ: −65.43 (s, 3F), −58.81 (s,3F); ESI-MS(+): 426 (M+H)⁺.

Step D:2-[4-Ethylsulfanyl-6-(Trifluoromethyl)Pyridazin-3-Yl]-3-Methyl-6-(Trifluoromethyl)Imidazo[4,5-b]Pyridine(Compound A1.014-B1.050)

4-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-6-(trifluoromethyl)pyridazine-3-carboxamide(369 mg, 0.9 mmol) in 10 ml of AcOH was refluxed for 2 hours. Then thereaction mixture was concentrated in vacuo. The residue was purified byflash column chromatography on silica gel to give2-[4-ethylsulfanyl-6-(trifluoromethyl)pyridazin-3-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine(compound A1.014-B1.050, 181 mg, 51%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.27(t, 3H), 3.20 (q, 2H), 4.07 (s, 1H), 8.12 (s, 1H). 8.75 (s, 1H), 8.93(s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−66.44 (s, 3F), −58.33 (s, 3F);ESI-MS(+): 408(M+H)⁺.)⁺. Mpt. 149-156° C. LCMS (SQD13) Rt. 1.12 min,408(M+H).

Step E:2-[4-ethylsulfonyl-6-(trifluoromethyl)pyridazin-3-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine(A1.014-B1.058)

A mixture of2-[4-ethylsulfanyl-6-(trifluoromethyl)pyridazin-3-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine(109 mg, 0.3 mmol) and m-CPBA (232 mg, 1.3 mmol) in 20 ml of CH₂Cl₂ wasstirred at room temperature for 2 h. Then the mixture was washed withsaturated sodium sulfite, aqueous sodium bicarbonate and dried oversodium sulfate. After filtration, the solvent was concentrated underreduced pressure. The residue was purified by flash chromatography onsilica gel to afford the title compound (compound A1.014-B1.058) (113mg, 96%). ¹HNMR (300 Mz, DMSO-d₆): δ 1.26 (t, 3H), 3.91 (s, 3H), 3.94(q, 2H), 8.77 (s, 1H), 8.79 (s, 1H), 8.97 (s, 1H); ¹⁹F-NMR (300 Mz,DMSO-d₆): δ−65.30 (s, 3F), −58.32 (s, 3F); ESI-MS(+): 440(M+H)⁺.) Mpt.172-174° C. LCMS (ZCQ13) Rt. 1.06 min, 440(M+H).

Example P4:5-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]thiazole(V13.05)

Step A ethyl 5-ethylsulfanylthiazole-4-carboxylate

A solution of ethyl isocyanoacetate (5.6 g, 0.05 mol) in 100 ml of THFwas added dropwise to a suspension of potassium t-butoxide (6.1 g, 0.055mol) in 20 ml of THF at −40° C. After the addition, the mixture wascooled to −60° C., carbon disulfide (3.8 g, 0.05 mol) was added dropwisewhile keeping the temperature below −50° C. Then, the mixture was warmedto 10° C. and ethyl bromide (5.4 g, 0.05 mol) was added. The mixture wasstirred for another 2 h and concentrated in vacuo. The residue waspurified by column chromatography on silica gel to afford the compoundethyl 5-ethylsulfanylthiazole-4-carboxylate (5.6 g, 52%). ¹H NMR (300MHz, DMSO-d₆): δ1.27-1.37 (m, 6H), 3.03 (q, 2H), 4.25 (q, 2H), 8.97 (s,1H); ESI-MS(+): 218(M+H)⁺, 240(M+Na)⁺.

Step B: 5-ethylsulfanylthiazole-4-carboxylic acid

A mixture of ethyl 5-ethylsulfanylthiazole-4-carboxylate (4.6 g, 0.02mol) and NaOH (1.68 mg, 0.04 mol) in 25 ml of water and 50 ml of THF wasstirred at room temperature overnight. Then, the reaction mixture waspoured into diluted hydrochloric acid. Then, the deposited precipitatewas filtered, washed with water, dried under reduced pressure to obtainthe title compound (3.9 g, 90%).

¹H NMR (300 MHz, DMSO-d₆): δ 1.32 (t, 3H), 3.00 (q, 2H), 8.94 (s, 1H),12.94 (br s, 1H); ESI-MS(+): 190(M+H)⁺, 212(M+Na)⁺; HPLC: 99.9%.

Step C: tert-butyl N-[4-amino-6-(trifluoromethyl)-3-pyridyl]carbamate:

To a solution of 6-(trifluoromethyl)pyridine-3,4-diamine (3.14 g, 17.73mmol, prepared as described in U.S. Pat. No. 7,767,687) in THF (50 ml)was added tert-butoxycarbonyl tert-butyl carbonate (4.64 g, 21.27 mmol)and the mixture was stirred at 50° C. After 8 hours, a further 1.1 g(5.0 mmol) of tert-butoxycarbonyl tert-butyl carbonate was added, andstirring at 50° C. continued for a further 4 hours. The reaction mixturewas then concentrated in vacuo, and the brown residue was suspended indichloromethane, filtered and dried in vacuo to give the title compoundas white crystals. LCMS (method SQD13): Ret. Time 0.79 min, 278 (M+H).

Step D: tert-butylN-[4-amino-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamate

To a stirred suspension of sodium hydride (0.648 g, 14.85 mmol) in 30 mlDMF, tert-butyl N-[4-amino-6-(trifluoromethyl)-3-pyridyl]carbamate (3.92g, 14.14 mmol) dissolved in 20 ml DMF was added dropwise over a periodof 20 min at 20-25° C. After 15 min stirring at RT, iodomethane (2.21 g,15.55 mmol) was added. After 30 min at ambient temperature the mixturewas poured onto 200 ml water, extracted twice with ethyl acetate, andthe combined organic fractions washed successively with water and brine,dried over Na₂SO₄ and concentrated in vacuo. The crude product wasrecrystallised from Ethyl acetate/Heptane to give the title compound(3.18 g) as white crystals. LCMS (method SQD13): ret. time 0.85 min, 292(M+H).

Step E: N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine

To a clear, colourless solution of tert-butylN-[4-amino-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamate (3.53 g,12.119 mmol) in dioxan, hydrogen chloride (18 ml of a 2M solution inwater, 36.36 mmol) was added and the mixture was heated to reflux. Aftergas evolution had ceased, the reaction mixture was cooled to roomtemperature, and treated with solid sodium hydrogen carbonate (3.1 g,36.9 mmol). The slurry was diluted with water and extracted twice withethyl acetate. The combined organic layers were washed successively withwater and brine, dried over Na₂SO₄ and concentrated in vacuo to give2.25 g of the title compound as colourless crystals, Mpt, 138-140° C.;LCMS (method SQD13): ret. Time 0.24 min, 192 (M+H).

Alternatively, N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine can beobtained by the following procedure:

To a solution of 6-(trifluoromethyl)pyridine-3,4-diamine (2.0 g, 12.2mmol) and potassium carbonate (3.2 g, 23.1 mmol) in acetonitrile (10 mL)was added iodomethane (0.8 mL). The reaction mixture was stirred at 30°C. overnight. Potassium carbonate was filtered off; the filtrate wasdried in vacuo and purified with chromatography column on silica gel(petroleum:EtOAc=4:3) to afford the title compound as a light yellowsolid (0.32 g, yield: 37%): ¹H NMR (400 MHz, DMSO-d₆): δ (ppm) 7.57 (s,1H), 6.83 (s, 1H), 5.82 (s, 2H), 5.23 (d, J=4.8 Hz, 1H), 2.80 (d, J=4.8Hz, 3H). ¹⁹F NMR (300 MHz, DMSO-d6): δ (ppm) −60.12 (s, 3F). ESI-MS(+):192 (M+H).

Step F:5-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]thiazole(Compound A6.002-B7.037)

A mixture of 5-ethylsulfanylthiazole-4-carboxylic acid (567 mg, 3 mmol),N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (483 mg, 3 mmol) andN-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC.HCL)(576 mg, 3.6 mmol) in 20 ml of pyridine was refluxed for 16 h. Thereaction mixture was concentrated in vacuo and purified by columnchromatography on silica gel to give title compound (120 mg),5-ethylsulfanyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]thiazole-4-carboxamide(51 mg and), andN-[4-amino-6-(trifluoromethyl)-3-pyridyl]-5-ethylsulfanyl-N-methyl-thiazole-4-carboxamide(162 mg). The latter two compounds were dissolved in 10 ml of AcOH andrefluxed for 16 h. Then the mixture was concentrated in vacuo and theresidue was purified by column chromatography on silica gel to giveadditional title compound (140 mg). ¹H NMR (400 MHz, DMSO-d₆): δ 1.34(t, 3H), 3.08 (q, 2H), 4.23 (s, 3H), 8.20 (s, 1H), 9.17 (s, 1H), 9.27(s, 1H); ¹⁹F-NMR (400 MHz, DMSO-d₆): δ−59.68 (s, 3F); ESI-MS: 345(M+H)⁺,367(M+Na)⁺; Mpt. 167-169° C.

Step G:5-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]thiazole(V13.05

5-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]thiazole(140 mg, 0.4 mmol) and m-CPBA (280 mg, 1.6 mmol) in 10 ml ofdichloromethane was stirred at room temperature for 0.5 h. Then themixture was poured into a saturated solution of Na₂CO₃ and Na₂SO₃ inwater, and extracted with ethyl acetate three times. The combinedorganic layers were dried over sodium sulfate, filtered and concentratedin vacuo. The residue was purified by column chromatography on silicagel to give the title compound (147 mg, 96%). ¹H NMR (400 MHz, DMSO-d₆):δ 1.28 (t, 3H), 4.04 (q, 2H), 4.05 (s, 3H), 8.32 (s, 1H), 9.29 (s, 1H),9.70 (s, 1H); ¹⁹F-NMR (400 MHz, DMSO-d₆): δ−58.84 (s, 3F); ESI-MS(+):377(M+H)⁺, 399(M+Na)⁺; LCMS (method SQD13) Rt. 0.85 min 377 (M+H). Mpt.178-179° C.

Example P5:2-[5-(difluoromethoxy)-3-ethylsulfonyl-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound V12.19)

Step A: 2,3-Dichloro-5-[(4-methoxyphenyl)methoxy]pyridine

A mixture 5,6-dichloropyridin-3-ol (8.2 g, 50 mmol),4-Methoxybenzylchloride (11.8 g, 75 mmol) and K₂CO₃ (21.0 g, 150 mmol)in CH₃CN (250 ml) was refluxed for 6 h. Then, the mixture was cooled toroom temperature and filtered. The filtrate was concentrated underreduced pressure and the residue was purified by column chromatographyon silica gel to give the title compound (10.0 g, 70% yield) as a whitesolid. ¹H NMR (400 MHz, DMSO-d₆): δ 3.72 (s, 3H), 5.09 (s, 2H), 6.92 (d,J=8.8 Hz, 2H), 7.35 (d, J=8.8 Hz, 2H), 7.89 (d, J=2.8 Hz, 1H), 8.15 (d,J=2.8 Hz, 1H); ESI-MS (+): 284(M+H)⁺; Mpt.: 124˜125° C.

Step B: Ethyl3-chloro-5-[(4-methoxyphenyl)methoxy]pyridine-2-carboxylate

CO gas was introduced to a mixture of2,3-dichloro-5-[(4-methoxyphenyl)methoxy]pyridine (10.0 g, 35.2 mmol),dppf (975 mg, 1.8 mmol), Pd(OAc)₂ (158 mg, 0.7 mmol) and Et₃N (10.2 ml,70.4 mmol) in 110 ml of EtOH, and the internal pressure was increased to1.6 MPa. The reaction mixture was stirred at 125° C. for about 7 hours.Then, the mixture was cooled to room temperature and filtered. Thefiltrate was concentrated under reduced pressure and the residue waspurified by column chromatography on silica gel to afford the titlecompound (6.8 g, 60% yield) as a light yellow solid. ¹H NMR (400 MHz,DMSO-d₆): δ 1.26 (t, J=6.8 Hz, 3H), 3.72 (s, 3H), 4.28 (q, J=6.8 Hz,2H), 5.15 (s, 2H), 6.92 (d, J=8.0 Hz, 2H), 7.37 (d, J=8.0 Hz, 2H), 7.76(d, J=2.0 Hz, 1H), 8.32 (d, J=2.0 Hz, 1H); ESI-MS (+): 322 (M+H)⁺, 345(M+Na)⁺; Mp: 45-46° C.

Step C: Ethyl3-ethylsulfanyl-5-[(4-methoxyphenyl)methoxy]pyridine-2-carboxylate

A mixture of ethyl3-chloro-5-[(4-methoxyphenyl)methoxy]pyridine-2-carboxylate (6.4 g, 0.02mol) and EtSNa (3.35 g, 0.04 mol) in 50 ml of DMF was stirred at 90° C.for 4 h. Then, the mixture was poured into water, and extracted withethyl acetate three times. The combined organic layers were dried oversodium sulfate, filtered and concentrated under reduced pressure. Theresidue was purified by column chromatography on silica gel to give thetitle compound (3 g, 43% yield). ¹H NMR (400 MHz, DMSO-d₆): δ 1.22 (t,3H), 1.29 (t, 3H), 2.97 (q, 2H), 3.76 (s, 3H), 4.27 (q, 2H), 5.24 (s,2H), 6.96 (d, 2H), 7.34 (d, 1H), 7.41 (d, 2H), 8.15 (d, 1H); ESI-MS(+):370(M+Na)⁺.

Step D:3-Ethylsulfanyl-5-[(4-methoxyphenyl)methoxy]pyridine-2-carboxylic acid

A mixture ofethyl-3-ethylsulfanyl-5-[(4-methoxyphenyl)methoxy]pyridine-2-carboxylate(3 g, 0.009 mol) and NaOH (692 mg, 0.017 mol) in 10 ml of water and 30ml of THF was stirred at room temperature overnight. Then, the reactionmixture was poured into diluted hydrochloric acid and extracted withethyl acetate three times. The combined organic layers were dried oversodium sulfate, filtered and concentrated in vacuo. The residue waspurified by flash column chromatography on silica gel to provide thetitle compound (2.3 g, 83% yield). ¹H NMR (400 MHz, DMSO-d₆): δ 1.23 (t,3H), 2.94 (q, 2H), 3.76 (s, 3H), 5.24 (s, 2H), 6.96 (d, 2H), 7.32 (d,1H), 7.41 (d, 2H), 8.13 (d, 1H), 12.69 (br s, 1H); ESI-MS(+): 320(M+H)⁺,342(M+Na)⁺.

Step E:3-Ethylsulfanyl-5-[(4-methoxyphenyl)methoxy]-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide

A mixture of compound3-ethylsulfanyl-5-[(4-methoxyphenyl)methoxy]pyridine-2-carboxylic acid(284 mg, 0.89 mmol), N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine(149 mg, 0.89 mmol, prepared as described in step E, example P4) andEDC.HCl (188 mg, 0.98 mmol) in 10 ml of pyridine was refluxed for 16 h.Then, the mixture was concentrated in vacuo, diluted with water, andextracted with ethyl acetate. The combined organic layers were driedover Na₂SO₄, concentrated under reduced pressure to give crude titleproduct (320 mg), which was directly used for the next step withoutfurther purification.

Step F:5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridin-3-ol

3-Ethylsulfanyl-5-[(4-methoxyphenyl)methoxy]-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide(320 mg) in 10 ml of AcOH was refluxed for 16 h. Then the mixture wasconcentrated in vacuo and the residue was purified by columnchromatography on silica gel to give the title compound (151 mg). ¹H-NMR(400 MHz, DMSO-d₆): δ 1.18 (t, 3H), 2.91 (q, 2H), 3.96 (s, 3H), 7.34 (d,1H), 8.11 (d, 1H), 8.22 (s, 1H), 9.18 (s, 1H), 10.74 (s, 1H); ¹⁹F-NMR(400 MHz, DMSO-d₆): δ−64.84 (s, 3F); ESI-MS(+): 355(M+H)⁺.

Step G:2-[5-(difluoromethoxy)-3-ethylsulfanyl-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine

At 50° C., CHCIF₂ gas was introduced to a mixture of5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridin-3-ol(100 mg, 0.28 mmol) and Cs₂CO₃ (460 mg, 1.41 mmol) in 10 ml of DMF for 2hours. Then, the mixture was poured into water, and extracted with ethylacetate three times. The combined organic layers were dried over sodiumsulfate, filtered and concentrated in vacuo. The residue was purified bycolumn chromatography on silica gel to give the title product (94 mg,82%). ¹H NMR (400 MHz, DMSO-d₆): δ 1.35 (t, 3H), 2.93 (q, 2H), 4.07 (s,3H), 6.67 (t, 1H), 7.52 (d, 1H), 8.19 (s, 1H), 8.36 (d, 1H), 8.95 (s,1H); ¹⁹F-NMR (400 MHz, DMSO-d₆): δ−81.81 (d, 1F), −66.25 (s, 3F);ESI-MS(+): 405(M+H)⁺, 427(M+Na)⁺, 459(M+MeOH+Na)⁺; HPLC: 98.2%

Step H:2-[5-(difluoromethoxy)-3-ethylsulfonyl-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound V12.19)

2-[5-(difluoromethoxy)-3-ethylsulfanyl-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(80 mg, 0.2 mmol) and m-CPBA (136 mg, 0.8 mmol) in 5 ml ofdichloromethane was stirred at room temperature for 0.5 h. Then themixture was poured into a saturated aqueous solution of Na₂CO₃ andNa₂SO₃, and extracted with ethyl acetate three times. The combinedorganic layers were dried over sodium sulfate, filtered and concentratedin vacuo. The residue was purified by column chromatography on silicagel to give the title compound (67 mg, 88%). ¹H NMR (400 MHz, DMSO-d₆):δ 1.19 (m, 3H), 3.78 (d, 3H), 3.90 (s, 3H), 6.77 (t, 1H), 8.11 (s, 2H),8.30 (d, 1H), 8.86 (d, 1H), 9.00 (s, 1H); ¹⁹F-NMR (400 MHz, DMSO-d₆):δ−78.62 (d, 1F), −62.07 (s, 3F); ESI-MS(+): 437(M+H)⁺. Mpt. 146-148° C.;LCMS (method SQD13): Ret. Time 1.03 mins, 405 (M+H).

Example P6:6-(2-Ethanesulfonyl-6-trifluoromethyl-pyridin-3-yl)-3-methyl-2-trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine(Compound V26.03)

Step A: 3-methyl-6-nitro-2-(trifluoromethyl)imidazo[4,5-b]pyridine

N2-methyl-5-nitro-pyridine-2,3-diamine (10 g, 59.52 mmol) in TFA (10 mL)was stirred at 70° C. for 16 h. The mixture was purified bychromatography on silica to get the pure title compound (9.81 g, 67%) asyellow solid. 1HNMR (300 MHz, d6-DMSO): δ 9.46 (d, J=2.4 Hz, 1H), 9.22(d, J=2.4 Hz, 1H), 4.04 (s, 3H).

Step B:3-methyl-6-nitro-4-oxido-2-(trifluoromethyl)imidazo[4,5-b]pyridin-4-ium

To a solution of3-methyl-6-nitro-2-(trifluoromethyl)imidazo[4,5-b]pyridine (5.3 g, 21.54mmol) in dichloromethanedichloromethane (60 ml) was added urea hydrogenperoxide (UHP, 6.17 g, 65.7 mmol), cooled with ice bath, and dropwiseadded TFAA (13.6 g, 65.7 mmol). The mixture was stirred at ambienttemperature for 18 hours. TCL showed about 50% of starting materialconsumed. Another batch of UHP (6.08 g, 64.63 mmol) and TFAA (13.8 g,64.63 mmol) was added at 0° C. The mixture was stirred at ambienttemperature for another 24 hours. The reaction mixture was diluted withwater, stirred and for 20 min. The organic phase was separated and theaqueous phase was back extracted with dichloromethane (3 times). Thecombined organic phases were washed with water and brine, dried overNa₂SO₄, and concentrated in vacuo. The residue was purified bychromatography on silica to give the title compound as a white solid(1.91 g). ¹HNMR (300 MHz, d6-DMSO): δ 9.17 (d, J=1.8 Hz, 1H), 8.83 (d,J=1.8 Hz, 1H), 4.41 (d, J=1.2 Hz, 3H).

Step C:5-chloro-3-methyl-6-nitro-2-(trifluoromethyl)imidazo[4,5-b]pyridine

3-methyl-6-nitro-4-oxido-2-(trifluoromethyl)imidazo[4,5-b]pyridin-4-ium(2.8 g, 10.69 mmol) was dissolved in POCl₃ (50 mL), and stirred atreflux for 2 hours. The mixture was poured into ice water, extractedwith EtOAc (3 times). The organic phase was washed with NaHCO₃ (aq) andwater, dried over Na₂SO₄, evaporated to dryness, to get the crude titlecompound (3.8 g) which used in the next step without furtherpurification.

Step D:N5,3-dimethyl-6-nitro-2-(trifluoromethyl)imidazo[4,5-b]pyridin-5-amine

To a solution of compound5-chloro-3-methyl-6-nitro-2-(trifluoromethyl)imidazo[4,5-b]pyridine (3.8g) in ethanol (40 mL) was added MeNH₂ (aq, 5 mL). The reaction mixturewas stirred at ambient temperature for 18 hours. The mixture wasfiltered, and dried in vacuo to get the pure title compound (2.3 g) as awhite solid. ¹HNMR (300 MHz, d6-DMSO): δ 8.90 (s, 1H), 8.64-8.62 (m,1H), 3.79 (d, J=1.2 Hz, 3H), 3.07 (d, J=4.8 Hz, 3H).

Step E:N5,3-dimethyl-2-(trifluoromethyl)imidazo[4,5-b]pyridine-5,6-diamine

To a solution of compoundN5,3-dimethyl-6-nitro-2-(trifluoromethyl)imidazo[4,5-b]pyridin-5-amine(2.3 g, 8.36 mmol) in EtOAc (30 mL) and methanol (30 mL) was added 200mg of palladium on carbon under N₂. The mixture was hydrogenated using ahydrogen balloon at rt for 4 h. The mixture was filtered through celiteand the filtrate was evaporated to dryness. The residue was purified bychromatography on silica to give the title compound (1.6 g, 78%) as apurple solid. ¹HNMR (300 MHz, d6-DMSO): δ 7.01 (s, 1H), 6.29 (d, J=3.3Hz, 1H), 4.69 (s, 2H), 3.77 (d, J=1.2 Hz, 3H), 2.92 (d, J=4.5 Hz, 3H).

Step F: 3-bromo-2-chloro-6-(trifluoromethyl)pyridine

A mixture of compound 2-chloro-6-(trifluoromethyl)pyridin-3-amine (5.88g, 30 mmol, prepared as described in WO 2009110475), isoamyl nitrite(7.02 g, 60 mmol), p-TsOH (6.19 g, 36 mmol), TBAB (19.32 g, 60 mmol) andCuBr₂ (1.40 g, 6 mmol) in 60 ml of MeCN was stirred at room temperaturefor 4 h. Then, the mixture was concentrated in vacuo and the residue waspurified by column chromatography on silica gel to give the titlecompound (5.85 g, 75%). ¹H-NMR (300 Mz, DMSO-d₆): δ 7.85 (d, 1H), 8.52(s, 1H); ¹⁹F-NMR (300 Mz, DMSO-d₆): δ−65.72 (s, 3F).

Step G: 3-bromo-2-ethylsulfanyl-6-(trifluoromethyl)pyridine

A mixture of 3-bromo-2-chloro-6-(trifluoromethyl)pyridine (5.98 g, 23mmol) and EtSNa (1.93 g, 23 mmol) in 50 ml of MeCN was stirred for 2 h.Then, the mixture was poured into dilute hydrochloric acid and extractedwith ethyl acetate three times. The combined organic layers were driedover sodium sulfate, filtered and concentrated in vacuo. The residue waspurified by column chromatography on silica gel to give the titlecompound (4.06 g, 58%). ¹H-NMR (300 Mz, DMSO-d₆): δ 1.26 (t, 3H), 3.08(q, 2H), 7.50 (d, 1H), 8.20 (d, 1H); ¹⁹F-NMR (300 Mz, DMSO-d₆): δ−65.45(s, 3F).

Step H: ethyl 2-ethylsulfanyl-6-(trifluoromethyl)pyridine-3-carboxylate

Carbon monoxide gas was introduced to a mixture of3-bromo-2-ethylsulfanyl-6-(trifluoromethyl)pyridine (572 mg, 2 mmol),Pd(OAc)₂ (90 mg, 0.4 mmol), dppf (444 mg, 0.8 mmol) and Et₃N (1.01 g, 10mmol) in 10 ml of EtOH and 10 ml of DMF and the internal pressure wasraised to 2.7 MPa. The mixture was heated at 90° C. for 6 h and cooledto room temperature. Then, it was poured into water and extracted withethyl acetate three times. The combined organic layers were dried oversodium sulfate, filtered and concentrated in vacuo. The residue waspurified by column chromatography on silica gel to give the titlecompound (795 mg, 88%). ¹H-NMR (300 Mz, DMSO-d₆): δ 1.23 (t, 3H), 1.28(t, 3H), 3.05 (q, 2H), 4.29 (q, 2H), 7.66 (d, 1H), 8.39 (d, 1H); ¹⁹F-NMR(300 Mz, DMSO-d₆): δ−62.88 (s, 3F).

Step I: 2-ethylsulfanyl-6-(trifluoromethyl)pyridine-3-carboxylic acid

A mixture of ethyl2-ethylsulfanyl-6-(trifluoromethyl)pyridine-3-carboxylate (480 mg, 1.7mmol) and KOH (482 mg, 8.6 mmol) in 10 ml of water and 10 ml of THF wasstirred at room temperature for 16 h. The reaction mixture was pouredinto diluted hydrochloric acid and extracted with ethyl acetate. Thecombined organic layers were dried over sodium sulfate, filtered andconcentrated in vacuo. The residue was purified by column chromatographyon silica gel to provide the title compound (430 mg, 90%). ¹H-NMR (300Mz, DMSO-d₆): δ 1.23 (t, 3H), 3.02 (q, 2H), 7.64 (d, 1H), 8.37 (d, 1H),13.85 (br s, 1H); ¹⁹F-NMR (300 Mz, DMSO-d₆): δ−62.78 (s, 3F); ESI-MS(−):250 (M−H)⁻.

Step J:2-ethylsulfanyl-N-[3-methyl-5-(methylamino)-2-(trifluoromethyl)imidazo[4,5-b]pyridin-6-yl]-6-(trifluoromethyl)pyridine-3-carboxamide

A mixture of 2-ethylsulfanyl-6-(trifluoromethyl)pyridine-3-carboxylicacid (251 mg, 1 mmol),N5,3-dimethyl-2-(trifluoromethyl)imidazo[4,5-b]pyridine-5,6-diamine (245mg, 1.0 mmol, product from step E in this example), HATU (570 mg, 1.5mmol) and DIPEA (258 mg, 2 mmol) in 10 ml of DMF was stirred for 16 h.The mixture was concentrated in vacuo and purified by columnchromatography on silica gel to give the title compound (408 mg, 84%).¹H NMR (300 Mz, DMSO-d₆): δ 1.26 (t, 3H), 2.91 (d, 3H), 3.07 (q, 2H),3.83 (s, 3H), 6.69 (q, 1H), 7.76 (d, 1H), 7.80 (s, 1H), 8.44 (d, 1H),9.97 (s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−62.50 (s, 3F), −57.02 (s,3F).

Step K:6-(2-Ethylsulfanyl-6-trifluoromethyl-pyridin-3-yl)-3-methyl-2-trifluoromethyl-3,5-dihydro-diimidazo[4,5-;4′,5′-e]pyridine

A mixture of2-ethylsulfanyl-N-[3-methyl-5-(methylamino)-2-(trifluoromethyl)imidazo[4,5-b]pyridin-6-yl]-6-(trifluoromethyl)pyridine-3-carboxamide(382 mg, 0.8 mmol) in 10 ml of AcOH was refluxed for 2 h, Then themixture was concentrated in vacuo and the residue was purified by columnchromatography on silica gel to give the title compound (231 mg, 63%).¹H-NMR (300 Mz, CDCl₃): δ 1.33 (t, 3H), 3.22 (q, 2H), 3.85 (s, 3H), 4.09(s, 3H), 7.51 (d, 1H), 7.86 (d, 1H), 8.59 (d, 1H); ¹⁹F NMR (300 Mz,CDCl₃): δ−68.64 (s, 3F), −63.72 (s, 3F); ESI-MS(+): 461(M+H)⁺, 483(M+Na)⁺. Mpt. 154-156° C.; LCMS; Ret. Time 1.13 mins, 461 (M+H)

Step L:6-(2-Ethanesulfonyl-6-trifluoromethyl-pyridin-3-yl)-3-methyl-2-trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine(Compound V26.03)

A mixture of6-(2-ethylsulfanyl-6-trifluoromethyl-pyridin-3-yl)-3-methyl-2-trifluoromethyl-3,5-dihydro-diimidazo[4,5-;4′,5′-e]pyridine(161 mg, 0.35 mmol) and m-CPBA (242 mg, 1.4 mmol) in 10 ml ofdichloromethane was stirred at room temperature for 2 h. Then themixture was poured into a saturated solution of NaHCO₃ and Na₂SO₃ inwater, and extracted with ethyl acetate three times. The combinedorganic layers were dried over sodium sulfate, filtered and concentratedin vacuo. The residue was purified by column chromatography on silicagel to give the title compound as a white solid (163 mg, 94%). ¹H NMR(300 Mz, CDCl₃): δ 1.30 (t, 3H), 3.53 (q, 2H), 3.85 (s, 3H), 4.09 (s,3H), 8.08 (d, 1H), 8.30 (d, 1H), 8.54 (s, 1H); ¹⁹F NMR (300 Mz, CDCl₃):δ−63.78 (s, 3F), −59.57 (s, 3F); ESI-MS: 493 (M+H)⁺, 515(M+Na)⁺. Mpt.197-199° C.; LCMS (method SQD13): Ret. Time 0.95 mins, 493 (M+H).

Example P7:4-Ethylsulfonyl-5-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole(Compound V14.05)

Step A: 4-bromo-2-(trifluoromethyl)thiazole

A mixture of 2,4-dibromothiazole (24.3 g, 0.1 mol), FSO₂CF₂COOCH₃ (23.0g, 0.12 mmol) and CuI (19.0 g, 0.1 mol) in 200 ml of DMF was heated for4 hours at 100° C. Then, the reaction mixture was poured into water andthe title compound (22.9 g, 83%) was distilled off at water pumppressure. The product was used without further purification in the nextstep.

Step B: 4-bromo-2-(trifluoromethyl)thiazole-5-carboxylic acid

At 60° C., n-BuLi (2.5M in hexane, 62 mmol) was slowly added to i-Pr₂NH(6 g, 59 mmol) in 150 ml of anhydrous THF under a nitrogen atmosphere.After the addition, the mixture was stirred at the same temperature foranother 0.5 hours. Then, 4-bromo-2-(trifluoromethyl)thiazole (12 g, 52.0mmol) was slowly added to the above mixture and stirring was continuedfor 20 min. The mixture was poured into dry ice and stirred for afurther hour. The reaction mixture was allowed to warm to ambienttemperature, diluted with ethyl acetate and the organic phase washedsuccessively with water and saturated brine, dried over sodium sulfate,filtered and concentrated under vacuum to give the title product (10.1g, 71%).

Step C: 4-bromo-2-(trifluoromethyl)thiazole-5-carbonyl chloride

A mixture of 4-bromo-2-(trifluoromethyl)thiazole-5-carboxylic acid (276mg, 1 mmol) in 10 ml of SOCl₂ was refluxed for 4 hours. The excess SOCl₂was distilled off to give the crude title product (295 mg) which wasdirectly used in the next step without further purification.

Step D:4-bromo-5-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole

A mixture of 4-bromo-2-(trifluoromethyl)thiazole-5-carbonyl chloride(477 mg, 1.7 mmol) and N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine(330 mg, 1.7 mmol, prepared as described in step E, example P4) in 10 mlof toluene was refluxed for 16 h. The reaction mixture was thenconcentrated in vacuo and the residue purified by column chromatographyon silica gel to give the title compound (358 mg, 44%). ¹H NMR (300 Mz,DMSO-d₆): δ: 3.98 (s, 3H), 8.30 (s, 1H), 9.28 (s, 1H); ¹⁹F NMR (300 Mz,DMSO-d₆): δ−61.58 (s, 3F), −57.88 (s, 3F); ESI-MS: 433 (M+H)⁺.

Step E:4-Ethylsulfanyl-5-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole

EtSNa (123 mg, 1.5 mmol) was added to a mixture of4-bromo-5-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole(315 mg, 0.7 mmol) in 10 ml of DMF. After the addition, the mixture wasstirred at room temperature for 2 hours. Then the mixture was pouredinto water and extracted with ethyl acetate three times. The combinedorganic layers were dried over sodium sulfate, filtered and concentratedunder reduced pressure. The crude product was purified by columnchromatography on silica gel to give the title compound (176 mg, 58%).¹H NMR (300 Mz, DMSO-d₆): δ 1.25 (t, 3H), 3.18 (q, 2H), 4.02 (s, 3H),8.25 (s, 1H), 9.24 (s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−59.80 (s, 3F),−55.95 (s, 3F); ESI-MS: 413(M+H)⁺. LCMS (method SQD13): Rt. 1.12 mins,413 (M+H) Mpt. 92-94° C.

Step F:4-ethylsulfonyl-5-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole(Compound V14.05)

A mixture of4-ethylsulfanyl-5-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole(109 mg, 0.3 mmol) and m-CPBA (228 mg, 1.3 mmol) in 15 ml of CH₂Cl₂ wasstirred for 2 h at room temperature. The reaction mixture was dilutedwith saturated sodium sulfite and aqueous sodium bicarbonate, and theorganic layer separated, dried over sodium sulfate, filtered andconcentrated in vacuo. The residue was purified by flash chromatographyon silica gel to give the title compound (71 mg, 61%). ¹H NMR (300 Mz,DMSO-d₆): δ 1.16 (t, 3H), 3.51 (q, 2H), 3.89 (s, 3H), 8.28 (s, 1H), 9.27(s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−59.81 (s, 3F), −55.74 (s, 3F);ESI-MS: 445(M+H)⁺, 467 (M+Na)⁺, 499 (M+MeOH+Na)⁺.

Example P8:4-ethylsulfonyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]thiazole(Compound V2.11)

Step A:4-bromo-N-methoxy-N-methyl-2-(trifluoromethyl)thiazole-5-carboxamide

A mixture of 4-bromo-2-(trifluoromethyl)thiazole-5-carboxylic acid (5.8g, 21 mmol, prepared as described as described in Step B, example P7),N,O-dimethylhydroxylamine hydrochloride (2.5 g, 25 mmol), HATU (9.6 g,25 mmol), and DIPEA (5.4 g, 42 mmol) in 35 ml of DMF was stirred at roomtemperature for 16 h. The mixture was poured into water and extractedwith ethyl acetate three times. The combined organic layers were driedover sodium sulfate, filtered and concentrated in vacuo. The residue waspurified by column chromatography on silica gel to give the titlecompound (4.7 g, 70%). ¹H NMR (300 Mz, DMSO-d₆): δ 3.27 (s, 3H), 3.68(s, 3H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−56.33 (s, 3F); ESI-MS: 341(M+Na)⁺.

Step B: 1-[4-bromo-2-(trifluoromethyl)thiazol-5-yl]ethanone

MeMgBr (3M in THF, 15 ml, 45 mmol) was added dropwise to a solution of4-bromo-N-methoxy-N-methyl-2-(trifluoromethyl)thiazole-5-carboxamide(5.7 g, 21 mmol) in 30 ml of dry THF under nitrogen atmosphere at 0° C.After the addition, the mixture was allowed to warm to ambienttemperature and stirred for 30 min. The mixture was then poured intodiluted hydrochloric acid and extracted with ethyl acetate three times.The combined organic layers were dried over sodium sulfate, filtered andconcentrated in vacuo. The residue was purified by flash chromatographyon silica gel to give the title product (4.8 g, 86%). ¹H NMR (300 Mz,DMSO-d₆): δ 2.68 (s, 3H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−66.14 (s, 3F).

Step C:4-bromo-2-(trifluoromethyl)-5-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]thiazole

A mixture of 1-[4-bromo-2-(trifluoromethyl)thiazol-5-yl]ethanone (220mg, 1 mmol), 2-amino-4-(trifluoromethyl)pyridine (193 mg, 1.2 mmol,prepared as described in WO 2011090122), Cu(OAc)₂.H₂O (12 mg, 0.1 mmol),1,10-Phenanthroline (18 mg, 0.1 mmol), Znl₂ (32 mg, 0.1 mmol) in 12 mlof dichlorobenzene was stirred at 120° C. for 16 h under an airatmosphere. The mixture was concentrated in vacuo and the residue waspurified by column chromatography on silica gel to give the titlecompound (153 mg, 36%). ¹H NMR (300 Mz, DMSO-d₆): δ 7.25 (d, 1H), 8.12(s, 1H), 8.84 (d, 1H), 8.96 (s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−64.34(s, 3F), −62.89 (s, 3F); ESI-MS(−): 414(M−H)⁻; HPLC: 97.7%.

Step D:4-ethylsulfanyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]thiazole

EtSNa (157 mg, 1.9 mmol) was added to a mixture of4-bromo-2-(trifluoromethyl)-5-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]thiazole(389 mg, 0.9 mmol) in 15 ml of DMF. After the addition, the mixture wasstirred at ambient temperature for 2 hours. The reaction mixture wasthen poured into water and extracted with ethyl acetate three times. Thecombined organic layers were dried over sodium sulfate, filtered andconcentrated in vacuo. The residue was purified by column chromatographyon silica gel to give the title compound (281 mg, 76%). ¹H NMR (300 Mz,DMSO-d₆): δ 1.28 (t, 3H), 3.23 (q, 2H), 7.24 (d, 1H), 8.11 (s, 1H), 8.75(s, 1H), 8.86 (d, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−66.81 (s, 3F),−65.09 (s, 3F); ESI-MS(+): 398(M+H)⁺; HPLC: 96.3%.

Step E:4-ethylsulfonyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]thiazole(Compound V2.11)

A mixture of4-ethylsulfanyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]thiazole(80 mg, 0.2 mmol) and m-CPBA (105 mg, 0.6 mmol) in 10 ml of CH₂Cl₂ wasstirred at ambient temperature for 2 hours. Then the mixture was washedwith saturated sodium sulfite and aqueous sodium bicarbonate. Theorganic layer was dried over sodium sulfate, filtered and concentratedin vacuo. The residue was purified by flash chromatography on silica gelto give the title compound (66 mg, 77%). ¹H NMR (300 Mz, DMSO-d₆): δ1.22 (t, 3H), 3.57 (q, 2H), 7.27 (d, 1H), 8.16 (s, 1H), 8.94 (d, 2H);¹⁹F NMR (300 Mz, DMSO-d₆): δ−48.60 (s, 3F), −50.52 (s, 3F); ESI-MS(+):430(M+H)⁺; HPLC: 96.9%. Mpt. 126-128° C.

Example P9:3-methyl-2-[3-methylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound V12.18)

Step A: 3-methylsulfonyl-5-(trifluoromethyl)pyridine-2-carbonyl chloride

3-methylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylic acid (1.0 g,3.7 mmol, prepared as described in US 20100234603) was suspended inSOCl₂ (5 mL), 1 drop of DMF was added to the mixture. The reactionmixture was heated to reflux, and stirred for 3 h. Then it wasevaporated to dryness under reduced pressure to give the title compoundas white solid (1.1 g, 100%). The residue was used directly for nextstep without further purification.

Step B:N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]-3-methylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxamide

To a solution of 3-methylsulfonyl-5-(trifluoromethyl)pyridine-2-carbonylchloride (80 mg, 0.3 mmol) in 5 ml of toluene was added compoundN3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (60 mg, 1.1 mmol,prepared as described in Step E, example P4), then the reaction mixturewas warmed to 100° C. for 5 hours. After that, it was cooled to roomtemperature and diluted with 15 ml of water and extracted three timeswith EtOAc. The combined organic layers were dried over sodium sulphateand purified by column chromatography on silica gel (EtOAc:Petroleumether=1/4) to give the title compound as a white solid (50 mg, 40%yield).

Step C:3-methyl-2-[3-methylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound V12.18)

5-methyl-N-[2-methyl-5-(methylamino)-4-pyridyl]-3-methylsulfonyl-pyridine-2-carboxamide(85 mg, 0.2 mmol) was added to 5 ml of acetic acid and the reactionmixture warmed to 100° C. for 12 h. The reaction mixture was cooled toroom temperature and diluted with 20 ml of water and extracted threetimes with EtOAc. The combined organic layers were dried over sodiumsulphate and purified by column chromatography on silica gel(EtOAc:Petroleum ether=1/4) to give the title compound as a white solid(40 mg, 50% yield). 1H NMR (300 MHz, CDCl₃) δ 3.65 (s, 3H), 3.94 (s,3H), 8.11 (s, 1H), 8.82 (s, 1H), 9.01 (s, 1H), 9.24 (s, 1H). ¹⁹F NMR(300 Mz, CDCl₃) δ−67.27 (s, 3H), δ−63.34 (s, 3H). ESI-MS: 425(M+1). Mpt.234-236° C. LCMS (method SQD 13) Rt. 0.93 min, 425 (M+H).

Example P10:2-[2-ethylsulfonyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine(Compound V3.05)

Step A: 2-ethylsulfanyl-6-(trifluoromethyl)pyridine-3-carbonyl chloride

A mixture of 2-ethylsulfanyl-6-(trifluoromethyl)pyridine-3-carboxylicacid (502 mg, 2 mmol, prepared as described in step I, example P6) in 10ml of SOCl₂ was refluxed for 4 hours. Then, the excess SOCl₂ wasevaporated to give the title compound (538 mg, 100%), which was directlyused for the next step without further purification.

Step B:2-ethylsulfanyl-N-methoxy-N-methyl-6-(trifluoromethyl)pyridine-3-carboxamide

A mixture of the crude product2-ethylsulfanyl-6-(trifluoromethyl)pyridine-3-carbonyl chloride (538 mg,2 mmol), N,O-dimethylhydroxylamine hydrochloride (588 mg, 6 mmol) andK₂CO₃ (1.66 g, 12 mmol) in 10 ml of THF and 1 ml of water was stirred atroom temperature for 10 min. Then, the mixture was poured into water andextracted with ethyl acetate three times. The combined organic layerswere dried over sodium sulfate, filtered and concentrated in vacuo. Theresidue was purified by column chromatography on silica gel to give thetitle compound (411 mg, y: 70%). ¹H-NMR (300 Mz, DMSO-d₆): δ 1.23 (t,3H), 3.10 (q, 2H), 3.23 (s, 3H), 3.45 (s, 3H), 7.64 (d, 1H), 7.94 (d,1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−62.44 (s, 3F).

Step C: 1-[2-ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl]ethanone

To a solution of2-ethylsulfanyl-N-methoxy-N-methyl-6-(trifluoromethyl)pyridine-3-carboxamide(411 mg, 1.4 mmol) in 10 ml of THF was added 1.4 ml of MeMgBr (3M inTHF) at room temperature and the reaction allowed to stir for 30 min.Then, the mixture was poured into water and extracted with ethyl acetatethree times. The combined organic layers were dried over sodium sulfate,filtered and concentrated in vacuo. The residue was purified by columnchromatography on silica gel to give the title compound (290 mg, y:83%). ¹H-NMR (300 Mz, DMSO-d₆): δ 1.22 (t, 3H), 2.60 (s, 3H), 3.02 (q,2H), 7.71 (d, 1H), 7.52 (d, 1H); ¹⁹F-NMR (300 Mz, DMSO-d₆): δ−67.93 (s,3F).

Step D:2-[2-ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine

A mixture of 1-[2-ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl]ethanone(249 mg, 1 mmol), 4-(trifluoromethyl)pyridin-2-amine (162 mg, 1.2 mmol),Cu(OAc)₂.H₂O (12 mg, 0.1 mmol), Znl₂ (32 mg, 0.1 mmol) and1,10-phenanthroline (18 mg, 0.1 mmol) in 5 ml of dichlorobenzene wasstirred at 130° C. for 48 h. Then the mixture was concentrated undervacuum and the residue was purified by column chromatography on silicagel to give the title compound (120 mg, y: 30%). ¹H NMR (300 Mz, CDCl₃):δ 1.39 (t, 3H), 3.29 (q, 2H), 7.00 (dd, 1H), 7.46 (d, 1H), 7.94 (s, 1H),8.27 (d, 1H), 8.42 (s, 1H), 8.47 (d, 1H); ¹⁹F NMR (300 Mz, CDCl₃):δ−69.33 (s, 3F), −64.83 (s, 3F); ESI-MS(+): 392 (M+H)⁺.

Step E:2-[2-ethylsulfonyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine(Compound V3.05)

A mixture of compound2-[2-ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine(156 mg, 0.4 mmol) and m-CPBA (277 mg, 1.6 mmol) in 10 ml ofDdichloromethane was stirred at ambient temperature for 2 hours. Thenthe mixture was poured into a saturated solution of NaHCO₃ and Na₂SO₃ inwater, and extracted with ethyl acetate three times. The combinedorganic layers were dried over sodium sulfate, filtered and concentratedin vacuo. The residue was purified by column chromatography on silicagel to give the title compound (115 mg, y: 68%)¹H-NMR (300 Mz, CDCl₃): δ1.50 (t, 3H), 3.74 (q, 2H), 7.01 (dd, 1H), 7.95 (s, 1H), 7.96 (d, 1H),8.27 (d, 1H), 8.77 (s, 1H), 8.92 (d, 1H); ¹⁹F NMR (300 Mz, CDCl₃):δ−73.07 (s, 3F), −69.08 (s, 3F); ESI-MS(+): 424(M+H)⁺. Mpt. 188-190° C.LCMS (method SQD 13): Rt. 1.07 mins, 424 (M+H).

Example P11:3-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-1,2,5-thiadiazole(Compound A1.014-B8.012)

Step A: ethyl (2Z)-2-cyano-2-hydroxyimino-acetate

H₃PO₄ (1.83 mL, 27 mmol) was added to a mixture of ethyl cyanacetate (5g, 44.2 mmol) and NaNO₂ (2.87 g, 41.5 mmol) in 35 mL of water at roomtemperature. After the addition, the mixture was warmed to 40° C. andstirred for another hour. Then, 3.69 ml of hydrochloric acid was addedto the mixture and stirring was continued for 18 hours. The mixture wasextracted with diethyl ether three times. The combined organic layerswere dried over sodium sulfate, filtered and concentrated under vacuum.The residue was purified by column chromatography on silica gel to givethe title compound (4.3 g, y: 69%) ¹H NMR (300 Mz, DMSO-d₆): δ 1.28 (t,3H), 4.32 (q, 2H).

Step B: ethyl 2-amino-2-cyano-acetate

Na₂S₂O₄ (17 g, 105 mmol) was slowly added to a mixture of ethyl(2Z)-2-cyano-2-hydroxyimino-acetate (5 g, 35 mmol) and NaHCO₃ (1.5 g, 17mmol) in 40 ml of water. Then the mixture was stirred at roomtemperature for 16 h and extracted with chloroform three times. Thecombined organic layers were dried over sodium sulfate, filtered andconcentrated under vacuum to give the title compound (3.18 g, y: 71%).¹H NMR (300 Mz, DMSO-d₆): δ 1.24 (t, 3H), 3.53 (s, 2H), 4.19 (q, 2H),4.81 (s, 1H).

Step C: ethyl 4-chloro-1,2,5-thiadiazole-3-carboxylate

Disulphur dichloride (4.06 g, 30 mmol) was added to a solution of ethyl2-amino-2-cyano-acetate (1.28 g, 10 mmol) in 10 ml of DMF at ambienttemperature. The mixture was stirred at ambient temperature for 16 h andpoured into ice, extracted three times with dichloromethane. Thecombined organic layers were dried over sodium sulfate, filtered andconcentrated under vacuum. The residue was purified by columnchromatography on silica gel to give the title compound (1.2 g, y: 63%).¹H NMR (300 Mz, DMSO-d₆): δ 1.35 (t, 3H), 4.39 (q, 2H).

Step D: ethyl 4-ethylsulfanyl-1,2,5-thiadiazole-3-carboxylate

Na₂S.9H₂O (2.4 g, 10 mmol) in 10 ml of water was added to a solution ofethyl 4-chloro-1,2,5-thiadiazole-3-carboxylate (1.92 g, 10 mmol) in 30mL of ethanol and the mixture was refluxed for 4 h. Then the mixture wasconcentrated in vacuo and a solution of bromoethane (3.24 g, 30 mmol) in10 ml of DMF was added. The reaction mixture was stirred at ambienttemperature for 16 hours, poured into dilute hydrochloric acid andextracted with ethyl acetate three times. The combined organic layerswere dried over sodium sulfate, filtered and concentrated under vacuum.The residue was purified by column chromatography on silica gel to givethe title compound (1.57 g, y: 72%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.34(t, 3H), 1.36 (t, 3H), 3.19 (q, 2H), 4.37 (q, 2H); ESI-MS (+): 219(M+H)⁺, 241 (M+Na)⁺.

Step E: 4-ethylsulfanyl-1,2,5-thiadiazole-3-carboxylic acid

A mixture of ethyl 4-ethylsulfanyl-1,2,5-thiadiazole-3-carboxylate (680mg, 3.12 mmol) and LiOH (240 mg, 10 mmol) in 5 ml of water and 5 ml ofTHF was stirred at room temperature for 2 h. Then, the reaction mixturewas poured into diluted hydrochloric acid and extracted with ethylacetate three times. The combined organic layers were dried over sodiumsulfate, filtered and concentrated in vacuo. The residue was purified bycolumn chromatography on silica gel to provide product the titlecompound (550 mg, y: 93%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.35 (t, 3H),3.12 (q, 2H).

Step F:3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-1,2,5-thiadiazole(Compound A1.014-B8.010)

A mixture of 4-ethylsulfanyl-1,2,5-thiadiazole-3-carboxylic acid (570mg, 3 mmol), N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (669 mg,3.5 mmol, prepared as described in WO 2012092051) and EDC.HCl (672 mg,3.5 mmol) in 5 ml of pyridine was refluxed for 16 h. Then, the mixturewas concentrated under vacuum and purified by column chromatography onsilica gel to give the title compound (621 mg, y: 60%). ¹H-NMR (300 Mz,DMSO-d₆): δ 1.41 (t, 3H), 3.27 (q, 2H), 4.24 (s, 3H), 8.73 (s, 1H), 8.90(s, 1H); ¹⁹F NMR (300 Mz, DMSO-d₆): δ−53.72 (s, 3F); ESI-MS(+): 346(M+H)⁺. LCMS (method SQD13): Rt. 1.21 mins, 346 (M+H) Mpt. 188-189° C.

Step G:3-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-1,2,5-thiadiazole(Compound A1.014-B8.012)

3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-1,2,5-thiadiazole(0.87 mmol, 300 mg) and m-CPBA (519 mg, 3 mmol) in 10 ml of DCM wasstirred at room temperature for 4 h. Then the mixture was poured into asaturated solution of NaHCO₃ and Na₂SO₃ in water, and extracted withethyl acetate three times. The combined organic layers were dried oversodium sulfate, filtered and concentrated in vacuo. The residue waspurified by column chromatography on silica gel to give the titlecompound (245 mg, 75%). ¹H NMR (300 Mz, DMSO-d₆): δ 1.31 (t, 3H), 3.97(q, 2H), 4.00 (s, 3H), 8.76 (s, 1H), 8.94 (s, 1H); ¹⁹F NMR (300 Mz,DMSO-d₆): δ−53.85 (s, 3F); ESI-MS(+): 378 (M+H)⁺, 400 (M+Na)⁺, 432(M+Na+MeOH)⁺. LCMS (method SQD13): Rt. 0.93 mins, 378 (M+H) Mpt.144-146° C.

Example P12:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)[1,2,4]triazolo[1,5-c]pyrimidine (Compound V16.03)

Step A: 4-(trifluoromethyl)pyrimidin-1-ium-1,6-diamine,2,4,6-trimethylbenzenesulfonate salt (MSH)

Caution: MSH is explosively unstable as a dry powder and is best handledin dichloromethane solution.

A Microwave tube, equipped with a magnetic stirrer bar, was charged with2,2,2-trifluoroacetic acid (4.4 g, 2.54 mmol, 2.9 mL). Then,(tert-butoxycarbonylamino) 2,4,6-trimethylbenzenesulfonate (1 g, 2.54mmol) was added at 0° C. The reaction mixture was stirred at 0° C. for 2h, ice-water was added and the precipitate was recovered by filtration.The wet cake was washed with water and dissolved in dichloromethane (5mL) and dried over sodium sulfate. The resulting solution was addeddropwise to a stirred solution of 6-(trifluoromethyl)pyrimidin-4-amine(0.3723 g, prepared as in WO2007113558) in dichloromethane (5 mL) at 0°C. After 1 hour at 0° C. and one night at RT (white suspension), thereaction mixture was diluted with diethyl ether (8 mL) and theprecipitate was recovered by filtration to afford the title compound(0.791 g, 82%).

Step B:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidine(Compound V16.03)

4-(trifluoromethyl)pyrimidin-1-ium-1,6-diamine,2,4,6-trimethylbenzenesulfonate salt (0.3 g, 0.791 mmol),3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylic acid (0.33593g, 1.1861 mmol) and3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine hydrochloride(0.1819098 g, 0.9489 mmol) was dissolved in pyridine (2 mL) and heatedfor for 3 h at 120° C. After this time, the reaction mixture was pouredon water, the aqueous layer was extracted three times with EtOAc. Thecombined organic layer were washed successively with water and brine,dried over Na₂SO₄, filtered and concentrated in vacuo. The crude productwas triturated with diethylether, and filtered to give the product as awhite powder (110 mg, 33%).

¹H NMR (400 MHz, CDCl3): δ (ppm) 9.31 (d, J=2.2 Hz, 1H), 9.17 (d, J=1.5Hz, 1H), 8.34-8.53 (m, 1H), 3.23 (q, J=7.5 Hz, 2H), 1.37 (t, J=7.5 Hz,3H). LCMS (method SQD13): Rt: 0.94 min, 426 (M+H). Mpt.: 190-192° C.

Example P13:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)oxazolo[5,4-c]pyridine(Compound V12.05)

Step A: 4-nitro-6-(trifluoromethyl)pyridin-3-ol

To a solution of 6-(trifluoromethyl)pyridin-3-ol (5.00 g, 30.7 mmol) insulfuric acid (92.0 mL) at 0° C. was added Ice (25.0 g, 1390 mmol)keeping the temperature below 10° C. To this solution was added nitricacid (2.97 g, 2.14 mL, 30.7 mmol) and the mixture was heated at 85° C.for 4 hours. A second portion of nitric acid (2.97 g, 2.14 mL, 30.7mmol) was added and the reaction was stirred over night at 85° C. LCMSanalysis showed ca. 40% conversion and thus nitric acid (2.97 g, 2.14mL, 30.7 mmol) was added and the reaction was stirred 5 h at 85° C. Afurther portion of nitric acid (2.97 g, 2.14 mL, 30.7 mmol) was addedand the reaction was stirred over night at 85° C. After this time, themixture was poured into ice water and extracted with 250 mL of Et₂O. Thecombined organic phases were dried over sodium sulfate and concentratedin vacuo. The residue was purified by flash chromatography, eluting withdichloromethane to give the title compound (18% yield). ¹H NMR (400 MHz,CDCl₃): 10.32 (s, 1H), 8.82 (s, 1H), 8.30 (s, 1H) ppm.

Step B: 4-amino-6-(trifluoromethyl)pyridin-3-ol

To a solution of 4-nitro-6-(trifluoromethyl)pyridin-3-ol (1.15 g, 5.53mmol) in ethanol (50 mL) and tetrahydrofuran (10 mL) was added Palladiumon carbon (0.12 g) under argon. A hydrogen atmosphere was applied(balloon) and the mixture was stirred over night at room temperature.After complete reduction, the mixture was filtered over celite and thecake washed with ethanol. The solvent was removed in vacuo and theresidue was purified by flash chromatography (cyclohexane/ethyl acetate)to give the title compound (0.98 g, quantitative) as a red gum. ¹H NMR(400 MHz, CDCl3): 7.92 (s, 1H), 6.92 (s, 1H), 4.75 (s, 2H) ppm.

Step C:2-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)oxazolo[5,4-c]pyridine.(Compound A6.006-B1.014)

To a solution of 4-amino-6-(trifluoromethyl)pyridin-3-ol (100 mg, 0.56mmol) and 3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxylic acid(155 mg, 0.62 mmol, prepared as described in WO 2013018928) inpolyphosphoric acid (2 mL) were stirred at 185° C. for 24 hours. Thereaction mixture was then poured into water (50 mL) under vigorousstirring, and the pH was adjusted to 8 with NaOH (2N). The aqueous phasewas extracted with dichloromethane (×2), and the combined organic phasesand dried over sodium sulphate. The solvent was evaporated in vacuo andthe residue was purified by flash chromatography (cyclohexane/ethylacetate) to give the title compound (75 mg, 34%).

¹H NMR (400 MHz, CDCl3): 9.20 (s, 1H), 8.82 (s, 1H), 8.32 (s, 1H), 7.98(s, 1H), 3.14 (q, 2H), 1.54 (t, 3H) ppm. LCMS (method SQD13): Rt: 1.15min, 394 (M+H).

Step D:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)oxazolo[5,4-c]pyridine(Compound V12.05)

To a solution of2-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)oxazolo[5,4-c]pyridine(60 mg, 0.153 mmol) in dichloromethane (10 mL) was added m-CPBA (83 mg,0.34 mmol). The resulting yellow solution was stirred for 1 hour at roomtemperature and then a further 60 mg of m-CPBA were added. The reactionmixture was stirred for a further 2 h at room temperature and thenpoured into a saturated solution of potassium carbonate. The aqueousphase was extracted 2 times with dichloromethane and the combinedorganic phases dried over sodium sulfate and concentrated in vacuo. Theresidue was purified by flash chromatography (cyclohexane/ethyl acetate)to give the title compound (49 mg, 75%) as a white powder (75%).

¹H NMR (400 MHz, CDCl₃): 9.28 (s, 1H), 9.22 (s, 1H), 8.84 (s, 1H), 8.24(s, 1H), 3.98 (q, 2H), 1.48 (t, 3H) ppm. LCMS (method SQD13): Rt. 1.02min, 426 (M+H+).

Example P14:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine(Compound V16.02)

Step A: 1-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]ethanone

A solution of bromo(methyl)magnesium (1.4 M in THF:Toluen 1:3, 14 MI,18.95 mmol) toluene dry (90 mL) was cooled to 0° C. and treated dropwisewith a solution of3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carbonitrile (4.00 g,17.23 mmol, prepared as described in WO 2013018928) dissolved in 30 mlof toluene. The reaction was allowed to stir for 30 min. at 0° C. LCMSanalysis after this time showed reaction completion. The reactionmixture was slowly quenched with NH₄Cl sat aq (50 ml) and HCl 10% (30ml) and the resulting mixture vigorously stirred for 15 min at roomtemperature. The aqueous layer was extracted twice with EtOAc, and thecombined organic phases washed successively with 10% HCl aq, water andbrine, dried over anhydrous Na₂SO₄, filtered and concentrated in vacuo.The crude title product (4.335 g, 91%) was used without purification forthe next step.

¹H NMR (400 MHz, CDCl₃): δ (ppm) 8.62 (s, 1H), 7.85 (d, J=1.1 Hz, 1H),2.96 (q, J=7.3 Hz, 2H), 2.74 (s, 3H), 1.43 (t, J=7.5 Hz, 3H). LCMS(method SQD13): Ret. Time 1.05 min, 250 (M+H).

Step B: 1-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]ethanone

At 0° C. m-CPBA (24.29 g, 98.53 mmol) was added portionwise to asolution of 1-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]ethanone(11.98 g, 48.06 mmol) in chloroform (400 mL) at 0° C. The resultingmixture was allowed to warm up to RT and stirred for 20 h. The reactionmixture was then quenched with 200 mL NaHCO₃ aq. and 50 mL saturatedsodium thiosulfate aqueous solution and extracted with three times withEtOAc. The combined organic phases were washed successively with aqueousNaHCO₃ and brine, dried over Na₂SO₄ and concentrated in vacuo.Purification on a 220 g column on the torrent machine eluting withEtOAc/heptane gave the title compound (8.5 g, 63%) as a white solid.

¹H NMR (400 MHz, CDCl₃): δ (ppm) 9.07 (d, J=1.1 Hz, 1H), 8.59 (d, J=1.5Hz, 1H), 3.58 (q, J=7.3 Hz, 2H), 2.74 (s, 3H), 1.38 (t, J=7.5 Hz, 3H).LCMS (method SQD13): Ret. Time 0.87 min, 282 (M+H).

Step C:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine

A mixture of 6-(trifluoromethyl)pyrimidin-4-amine (232 mg, 1.0607 mmol,prepared as described in WO2007113558),1-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]ethanone (200 mg, 0.71mmol), copper(I)iodide (7.0 mg, 0.036 mmol), In(III)triflate (4.0 mg,0.0071 mmol) and 1-methyl-2-pyrrolidone (4 mL) were stirred for 19 hr at120° C. LC-MS: desired product and starting material, and thus thereaction was stirred for a further 27 hr at 120° C. Reaction mixture wascooled to ambient temperature and water and ethylacetate were added.Aqueous layer was extracted 2 times with ethylacetate and the combinedorganic layers were washed with brine, dried over Na2SO4, filtered andconcentrated in vacuo. The product was purified by combiflashchromatography with column of 12 g and a gradient of cyclohexane+0-80%ethylacetate, to give the title compound (96 mg, 31%) as a white solid.¹H NMR (400 MHz, CDCl₃): δ (ppm) 9.20 (s, 1H), 9.14 (s, 1H), 8.80 (d,J=1.5 Hz, 1H), 8.44 (s, 1H), 7.99 (s, 1H), 4.10 (q, J=7.5 Hz, 2H), 1.43(t, J=7.5 Hz, 3H). LCMS (method SQD13): Rt: 0.98 min, 425 (M+H). Mpt.180-181° C.

Example P15:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine(Compound V16.01)

Step A:3-bromo-2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine

2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine(52 mg, 0.123 mmol) was dissolved in acetonitrile (1 mL) and treatedwith N-bromosuccinimide (24.5 mg, 0.135 mmol) at ambient temperature.Reaction mixture was stirred over night at room temperature. Thereaction mixture was concentrated in vacuo and purified by combiflashchromatography with a column of 4 g and a gradient cyclohexane+0-50%ethylacetate. The title product was obtained as a white solid.

¹H NMR (400 MHz, CDCl₃): δ (ppm) 9.22 (d, J=0.7 Hz, 1H), 9.20 (s, 1H),8.77 (d, J=1.5 Hz, 1H), 7.94 (s, 1H), 4.00 (q, J=7.6 Hz, 2H), 1.40-1.47(t, J=7.6 Hz, 3H). LCMS (method SQD13): Rt: 1.04 min, 503/505 (M+H).

Step B:3-bromo-2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine(Compound V16.01)

A suspension of3-bromo-2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine(100 mg, 0.199 mmol) and potassium carbonate (84 mg, 0.60 mmol) in1,4-dioxane (3 mL) was purged with argon for 10 min and then treatedwith 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (30.0 mg, 0.24 mmol,0.0332 mL) and Pd(Ph3)4 (23 mg, 0.02 mmol). The reaction mixture washeated at 95° C. for 12 hr. LCMS analysis showed the desired product andstarting material, and thus the mixture was cooled and purged with argonfor 10 min and treated with2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (30.0 mg, 0.24 mmol,0.0332 mL) and Pd(Ph3)4 (23 mg, 0.02 mmol). The reaction mixture washeated for a further 5 hr 95° C. until reaction completion. The reactionmixture was diluted with NH₄Cl sat sol, and water, and then extractedthree times with ethyl acetate. The combined organic layers were washedwith brine, dried over Na2SO4, filtered and concentrated in vacuo. Theproduct was purified by Combiflash chromatography with a column of 12 gand a gradient cyclohexane 0-50% ethylacetate. This gave the titleproduct (51 mg, 59%) as a white solid. ¹H NMR (400 MHz, CDCl₃): δ (ppm)9.17 (d, J=1.5 Hz, 1H), 9.01 (s, 1H), 8.77 (d, J=1.5 Hz, 1H), 4.10 (q,J=7.6 Hz, 2H), 2.78 (s, 3H), 1.40-1.47 (t, 7.6 Hz, 3H). LCMS (methodSQD13): Rt: 1.01 min, 439 (M+H). Mpt. 240-242° C.

Example P16:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-1-methyl-5-(trifluoromethyl)imidazo[4,5-b]pyrazine(Compound A1.026-B1.022)

Step A: 3,5-diiodo-N-methyl-pyrazin-2-amine

To a stirred solution of N-methylpyrazin-2-amine (1 g, 9.2 mmol) indimethyl sulfoxide (20 ml)/water (0.4 ml) at 10° C. was addedportionwise N-Iodosuccinimide (4.1 g, 18.4 mmol). The reaction mixturewas then allowed to warm slowly to room temperature and stirred at thattemperature overnight. An additional aliquot of N-Iodosuccinimide (4.1g, 18.4 mmol) was then added at room temperature. After stirring for 7hr, the reaction mixture was poured onto ice (20 g). The precipitate wascollected, washed with cold water (20 ml), and dried to provide thetitle compound (2.15 g, 65%). ¹H NMR (300 MHz, DMSO-d₆) δ (ppm): 8.14(s, 1H), 6.69 (br, 1H), 2.77 (d, 3H, J=4.5 Hz); ESI-MS(−): 360.

Step B: 5-iodo-N2-methyl-pyrazine-2,3-diamine

NH₃(g) in EtOH (15 ml) was added to 3,5-diiodo-N-methyl-pyrazin-2-amine(2.15 g, 6 mmol) and the mixture was heated to 150° C. in a sealed tubefor 18 h. After the solution was cooled, dichloromethane and water (1:1,200 ml) were added. The aqueous phase was extracted with methylenechloride (50 ml) and the combined organic layers were dried over Na₂SO₄and concentrated to give the title compound as a white solid. (1.19 g,80%). ¹H NMR (300 MHz, DMSO-d₆) δ (ppm): 7.41 (s, 1H) 6.35 (br, 3H),2.78 (s, 3H); ESI-MS (−): 249, ESI-MS (+): 251.

Step C:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-5-iodo-1-methyl-imidazo[4,5-b]pyrazine

This compound was prepared by methods described in the examples abovefrom 5-iodo-N2-methyl-pyrazine-2,3-diamine and3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylic acid.

Step D:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-1-methyl-5-(trifluoromethyl)imidazo[4,5-b]pyrazine(Compound A1.026-B1.022)

A mixture of compound2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-5-iodo-1-methyl-imidazo[4,5-b]pyrazine(497 mg, 1 mmol), FSO₂CF₂COOMe (384 mg, 2 m mol) and CuI (191 mg, 1mmol) in 5 ml of DMF was stirred at 120° C. under an nitrogen atmospherefor 24 h. Then the mixture was poured into dilute hydrochloric acid andextracted with ethyl acetate three times. The combined organic layerswere dried over sodium sulfate, filtered and concentrated under vacuum.The crude product was purified by column chromatography on silica gel togive the title compound (197.5 mg, Y: 45%). ¹H NMR (300 MHz, CDCl₃) δ(ppm): 9.26 (s, 1H), 8.88 (s, 1H), 8.75 (s, 1H), 3.98 (m, 5H), 1.42 (t,J=6.9 Hz, 3H). ¹⁹F NMR (300 Mz, CDCl₃) δ (ppm): −62.15; −65.18. ESI-MS:440(M+H), 462(M+Na⁺). Mpt. 162-165° C. LCMS (method SQD13): Rt. 1.04mins, 440 (M+H).

Example P17:3-methyl-2-[3-(methylsulfonylmethyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5-b]pyridine(Compound A.014-B1.106)

Ethyl 3-methyl-5-(trifluoromethyl)pyridine-2-carboxylate (1.0 g 4.29mmol, prepared as described in J. Amer. Chem. Soc., 2013, 135,12122-12134) was dissolved in acetonitrile (40 ml) and treated withN-bromsuccinamide (1.21 g, 6.43 mmol) and benzoyl peroxide (0.150 g,0.600 mmol). A sunlamp was used to irradiate the reaction mixture whichwas heated at reflux (75° C. bath temp.) After 10 hr, the mixture wascooled, filtered, and concentrated in vacuo. The crude product (1.27 g),which contained mainly ethyl3-(bromomethyl)-5-(trifluoromethyl)pyridine-2-carboxylate, was used inthe next step without further purification.

Ethyl 3-(bromomethyl)-5-(trifluoromethyl)pyridine-2-carboxylate (0.5 g,1.6 mmol, prepared as above) was dissolved in DMF, cooled to 0° C., andtreated with sodium methanethiolate (0.22 g, 3.2 mmol) The mixture wasallowed to warm up to RT and was stirred over night. The reactionmixture was diluted NH₄Cl aq., and extracted with TBME (2×). Theremaining aqueous layer was acidified with 6N HCl aq and extracted 3×with dichloromethane. The combined dichloromethane layers were driedover Na₂SO₄, filtered and evaporated to give 0.31 g of a beige solid,which contains the desired3-(methylsulfanylmethyl)-5-(trifluoromethyl)pyridine-2-carboxylic acid.This was used in the next step without further purification.

N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (0.24 g, 1.3 mmol,prepared as described in WO 2012092051), EDC.HCl (0.24 g, 1.3 mmol) and3-(methylsulfanylmethyl)-5-(trifluoromethyl)pyridine-2-carboxylic acid(0.29 g, crude sample from above) were dissolved in pyridine (15 ml).The brown suspension was stirred at 120° C. for 2 h. The reactionmixture was diluted with water, and extracted EtOAc. The organic layerwas separated and washed with brine, dried over Na2SO4 and evaporated.The crude product was purified by chromatography on an RF 200 machineeluting with EtOAc/Cylohexane gradient, to give 0.35 g of a beige solid,which contained the desired productN-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-3-(methylsulfanylmethyl)-5-(trifluoromethyl)pyridine-2-carboxamide.This product was dissolved in 1-methylpyrrolidin-2-one (5 ml) withtoluene-4-sulphonic acid (0.072 g, 0.41 mmol) and heated in themicrowave at 160° C. for 1 h. After this time, the reaction mixture wasdiluted with water, and extracted with EtOAc. The organic layer waswashed with water and brine, dried over sodium sulfate and concentratedin vacuo. Purification over a silica gel cartridge (Rf200), eluting withCyclohexane/EtOAc gave3-methyl-2-[3-(methylsulfanylmethyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5-b]pyridine(140 mg) as a white solid. LCMS (method SQD13): Rt. 1.17 mins, 407(M+H).

A solution of3-methyl-2-[3-(methylsulfanylmethyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5-b]pyridine(100 mg, 0.25 mmol) in dichloromethane was cooled to 0° C. and MCPBA (61mg, 0.25 mmol) was added at 0° C. LC/MS after 1 h showed sulphoxide andsulphone and thus a further 61 mg of MCPBA was added. Upon reactioncompletion, the mixture was quenched 2M Na₂CO₃ and dichloromethane. Theorganic layer was separated, washed once with water, dried over Na₂SO₄,filtered and concentrated in vacuo. Purification over a silica gelcartridge (Rf200), eluting with Cyclohexane/EtOAc gave the titlecompound (80 mg, 70%) as a white solid. LCMS (method SQD13): Rt. 1.02mins, 439 (M+H). ¹H NMR (400 MHz, CDCl₃): δ (ppm) 9.08 (d, J=1.5 Hz,1H), 8.79 (d, J=1.5 Hz, 1H), 8.34-8.36 (m, 1H), 8.33 (d, J=1.8 Hz, 1H),5.25 (s., 2H), 4.13 (s, 3H), 2.93 (s, 3H).

Example P18:6-bromo-2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-imidazo[4,5-c]pyridine(Compound V12.20)

Step A: 2-bromo-5-fluoro-1-oxido-pyridin-1-ium

To a stirred solution of 2-bromo-5-fluoropyridine (5.0 g, 28.4 mmol) inTFA (10.0 mL) was added H₂O₂ (30%, 15 mL) dropwise at 0° C., the mixturewas stirred under reflux overnight. After cooling, the reaction systemwas poured onto ice-water, extracted with dichloromethane/methanol(10:1, 50 mL×3), the organic layer was washed with saturated sodiumbicarbonate solution and brine, and dried over anhydrous sodium sulfate.After filtration and concentration in vacuo, the crude product (offwhite solid, 4.6 g, y: 84%) was used for the next step without furtherpurification.

Step B: 2-bromo-5-fluoro-4-nitro-1-oxido-Pyridin-1-ium

To a solution of 2-bromo-5-fluoro-1-oxido-pyridin-1-ium (4.6 g, 23.9mmol) in sulphuric acid (conc.) (20 mL) was added fuming nitric acid (10mL) slowly at 0° C. After the addition the reaction temperature wasraised to 120° C., and stirring continued at this temperature for 4 h.After cooling to room temperature, the reaction solution was poured ontoice-water. The pH value was adjusted to 1 with NH₄OH. The precipitatewas filtered and oven dried to afford the title compound (2.3 g, 40%) aslight yellow solid.

Step C: 6-bromo-N-methyl-4-nitro-1-oxido-pyridin-1-ium-3-amine

To a solution of 2-bromo-5-fluoro-4-nitro-1-oxido-pyridin-1-ium (1.1 g,4.6 mmol) in ethanol (10 mL) was added MeNH₂/ethanol (4 mL). Thereaction mixture was stirred at room temperature for 4 h. The mixturewas concentrated in vacuo to give the title compound as a solid whichwas used for the next step without further purification.

Step D: 6-bromo-N-methyl-4-nitro-pyridin-3-amine

To a solution of 6-bromo-N-methyl-4-nitro-1-oxido-pyridin-1-ium-3-amine(crude from above, 4.6 mmol) in dichloromethane (10 mL) was added PBr₃(1.0 mL). The reaction mixture was stirred at ambient temperature for 1hour. The mixture was dried under vacuum to give the title compound as ajacinth solid and used for the next step without further purification.

Step E: 6-bromo-N3-methyl-pyridine-3,4-diamine

To a solution of 6-bromo-N-methyl-4-nitro-pyridin-3-amine (crude, 4.6mmol) in methanol (10 mL) was added Raney Ni (20% wt), and hydrazinehydrate (1.0 mL) was added dropwise at 0° C. The reaction mixture wasstirred at room temperature for a few minutes. Raney Ni was filtered offthrough celite; the filtrate was dried in vacuo and purified withchromatography column on silica gel (dichloromethane:methanol, 10:1) toafford the title compound as a light purple solid (0.6 g, three-stepyield, 63%). ¹H NMR (400 MHz, DMSO-d₆): δ (ppm) 7.20 (s, 1H), 6.65 (s,1H), 6.54 (brs, 2H), 3.34 (s, 1H), 2.69 (d, J=6.4 Hz, 3H). ESI-MS(+):203 (M+H).

Step F:N-(4-amino-6-bromo-3-pyridyl)-3-ethylsulfonyl-N-methyl-5-(trifluoromethyl)pyridine-2-carboxamide

To a stirred solution of 6-bromo-N3-methyl-pyridine-3,4-diamine (0.60 g,2.96 mmol), 3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylicacid (0.92 g, 3.26 mmol, prepared as in WO 2013180194) and HATU (1.4 g,3.68 mmol) in DMF (5.0 mL) was added DIPEA (1.2 ml, 7.26 mmol). Thesystem was stirred at room temperature overnight. The reaction wasdiluted with EtOAc and H₂O, the organic layer was washed with brine andwater, dried over anhydrous sodium sulfate. After filtration andconcentration in vacuo, the crude title product was used for the nextstep without further purification.

Step G:6-bromo-2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-imidazo[4,5-c]pyridine(Compound V12.20)

A solution ofN-(4-amino-6-bromo-3-pyridyl)-3-ethylsulfonyl-N-methyl-5-(trifluoromethyl)pyridine-2-carboxamide(crude, 2.96 mmol) in acetic acid (5.0 mL) was stirred at 120° C.overnight. The mixture was evaporated to dryness. The residue waspurified by chromatography on silica gel (Petroleum ether:EtOAc=4:1) toafford the title compound as white solid (0.65 g, two-step yield: 48%).¹H NMR (400 MHz, DMSO-d₆): δ (ppm) 9.53 (s, 1H), 8.94 (s, 1H), 8.74 (s,1H), 8.01 (s, 1H), 3.83 (q, J=7.6 Hz, 2H), 3.79 (s, 3H), 1.19 (t, J=7.2Hz, 3H). ¹⁹F NMR (300 MHz, DMSO-d₆): δ (ppm) −60.42 (s, 3F). ESI-MS(+):449 (M+H), 472(M+Na); ESI-MS(−): 447 (M−H). Mpt. 188-190° C. LCMS(method SQD13): Rt. 0.95 min, 449/451 (M+H).

Example P19:3-chloro-6-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazo[4,5-c]pyridazine(Compound V12.17)

Step A: 3,6-dichloropyridazin-4-amine

4-Bromo-3,6-dichloro-pyridazine (15.0 g, 65.8 mmol, prepared asdescribed in WO 2008116815) was dissolved in EtOH (73.1 mL) andintroduced into an autoclave. At rt, gaseous NH3 (4.48 g, 263 mmol) wasintroduced, and the reaction mixture was then stirred over night atreflux. The solution was concentrated in vacuo and the residue wastriturated with EtOAc, the insoluble part was filtrated off, and themother liquor evaporated to give the crude product. This was purified byFlash-Chromatography, eluting with cyclohexan/EtOAc 1/1+2.5% Et3N, togive the title compound as a pale brown solid (5.82 g, 53%). LCMS(method ZCQ13): Rt. 0.3 min, 164/166/168 (M+H).

Step B: 6-chloro-N3-methyl-pyridazine-3,4-diamine

In an autoclave, 3,6-dichloropyridazin-4-amine (2.35 g, 14.3 mmol) wastreated with Methylamine dissolved in EtOH (20.2 g, 215 mmol, 26.7 mL)and heated to 100° C. After 48 h at 100° C. LCMS showed no more startingmaterial. The reaction mixture was evaporated to dryness. The crudeproduct was diluted in dichloromethane and 4 ml Et₃N was added. Themixture was stirred 5′ at rt and evaporated. The residue was dilutedwith 5 ml water and the insoluble material was filtrated and dried togive the title product 1.35 g, 57%) as a pale brown solid. LCMS (MethodZCQ13): Rt. 0.17 min, 157/159 (M−H).

Step C:N-[6-chloro-3-(methylamino)pyridazin-4-yl]-3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxamide

6-Chloro-N3-methyl-pyridazine-3,4-diamine (0.3 g, 1.89 mmol) dissolvedin Pyridine (14.6 mL), was treated with3-Ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxylic acid (0.499 g,1.99 mmol, prepared as described in WO 2013018928) and EDCI.HCl (0.4352g, 2.27 mmol). The reaction mixtures was stirred 4 h at rt, and thentreated with a further portion of EDCI.HCl (0.4352 g, 2.27 mmol). Themixture was stirred over night at rt. The reaction mixture was thenconcentrated in vacuo and the residue taken up in EtOAc and water. Thephases were separated and the organic phase washed with brine, driedover Na₂SO₄, and concentrated in vacuo. The crude product was purifiedby Flash-Master (Solvent: Cyclohexan/EtOAc 3/1 to give the titlecompound as a white solid (250 mg, 33%). LCMS (method ZCQ13) Ret. Time1.01 min, 392/394(M+H).

Step D:3-chloro-6-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazo[4,5-c]pyridazine(Compound A6.015-B1.014)

N-[6-chloro-3-(methylamino)pyridazin-4-yl]-3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxamide(250 mg, 0.64 mmol) was dissolved in DMF (2 mL) and toluene (8 mL).p-toluenesulfonic acid monohydrate (0.123 g, 0.70 mmol) was added. Thebombe tube was closed, and heated to 160° C. for 4 hr. This was thencooled to rt and evaporated to dryness. The residue was purified byFlash-Master (Solvent: Cyclohexan/EtOAc 2/1) to give the title compound(172 mg, 72%) as a yellow solid.

¹H NMR (400 MHz, CDCl₃): δ (ppm) 8.65-8.88 (m, 1H), 7.86-8.05 (m, 2H),4.13-4.27 (m, 3H), 3.04 (q, J=7.5 Hz, 2H), 1.41 (t, J=7.5 Hz, 3H). LCMS(method ZCQ13): Ret. Time 1.01 min, 374/376(M+H). Mpt.: 156°-158° C.

Step D:3-chloro-6-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazo[4,5-c]pyridazine(Compound V12.17)

3-chloro-6-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazo[4,5-c]pyridazine(0.14 g, 0.3745 mmol) was dissolved in dichloromethane (8 mL). At 0° C.MCPBA (0.1747 g, 0.7491 mmol) was added, and the mixture was stirred 1 hat 0° C., then 3 h at rt. The reaction was quenched with sat sodiumthiosulphate solution. The separated organic phase was washed with aqNaHCO₃ and brine, dried over Na₂SO₄, filtrated and concentrated invacuo. The crude product was purified by Flash-Master (Solvent:Cyclohexan/EtOAc 1/1) to give the title compound (164 mg, 96%) as awhite solid. ¹H NMR (400 MHz, CDCl₃): δ (ppm) 9.28 (d, J=1.5 Hz, 1H),8.78 (d, J=1.8 Hz, 1H), 7.71-8.03 (m, 1H), 4.02 (s, 3H), 3.84 (q, J=7.6Hz, 2H), 1.40 (t, J=7.5 Hz, 3H). LCMS (method ZCQ13): Ret. Time 0.91min, 406/408 (M+H). Mpt. 228-229° C.

Specific examples of compounds of formula (I) are illustrated in theTables 1 to 130 below, wherein Tables A to K depict the groups B andTables L to Q depict groups A:

A-B  (I)

TABLE A Radicals of formula B₁ (DB denotes a direct bond, i.e. thesulphur is attached directly to the aromatic ring) B₁

Radical R₃ R₄ V₀ V₁ V₂ m L₁ B1.001 CH₃ H C—H N C—H 0 DB B1.002 CH₃ H C—HN C—CF₃ 0 DB B1.003 CH₃ H C—H N C—Br 0 DB B1.004 CH₃ H C—H N C—Cl 0 DBB1.005 CH₃ H C—H N C—H 1 DB B1.006 CH₃ H C—H N C—CF₃ 1 DB B1.007 CH₃ HC—H N C—Br 1 DB B1.008 CH₃ H C—H N C—Cl 1 DB B1.009 CH₃ H C—H N C—H 2 DBB1.010 CH₃ H C—H N C—CF₃ 2 DB B1.011 CH₃ H C—H N C—Br 2 DB B1.012 CH₃ HC—H N C—Cl 2 DB B1.013 CH₂CH₃ H C—H N C—H 0 DB B1.014 CH₂CH₃ H C—H NC—CF₃ 0 DB B1.015 CH₂CH₃ H C—H N C—Br 0 DB B1.016 CH₂CH₃ H C—H N C—Cl 0DB B1.017 CH₂CH₃ H C—H N C—H 1 DB B1.018 CH₂CH₃ H C—H N C—CF₃ 1 DBB1.019 CH₂CH₃ H C—H N C—Br 1 DB B1.020 CH₂CH₃ H C—H N C—Cl 1 DB B1.021CH₂CH₃ H C—H N C—H 2 DB B1.022 CH₂CH₃ H C—H N C—CF₃ 2 DB B1.023 CH₂CH₃ HC—H N C—Br 2 DB B1.024 CH₂CH₃ H C—H N C—Cl 2 DB B1.025 CH₃ H C—H CH C—H0 DB B1.026 CH₃ H C—H CH C—CF₃ 0 DB B1.027 CH₃ H C—H CH C—Br 0 DB B1.028CH₃ H C—H CH C—Cl 0 DB B1.029 CH₃ H C—H CH C—H 1 DB B1.030 CH₃ H C—H CHC—CF₃ 1 DB B1.031 CH₃ H C—H CH C—Br 1 DB B1.032 CH₃ H C—H CH C—Cl 1 DBB1.033 CH3 H C—H CH C—H 2 DB B1.034 CH3 H C—H CH C—CF₃ 2 DB B1.035 CH3 HC—H CH C—Br 2 DB B1.036 CH3 H C—H CH C—Cl 2 DB B1.037 CH₂CH₃ H C—H CHC—H 0 DB B1.038 CH₂CH₃ H C—H CH C—CF₃ 0 DB B1.039 CH₂CH₃ H C—H CH C—Br 0DB B1.040 CH₂CH₃ H C—H CH C—Cl 0 DB B1.041 CH₂CH₃ H C—H CH C—H 1 DBB1.042 CH₂CH₃ H C—H CH C—CF₃ 1 DB B1.043 CH₂CH₃ H C—H CH C—Br 1 DBB1.044 CH₂CH₃ H C—H CH C—Cl 1 DB B1.045 CH₂CH₃ H C—H CH C—H 2 DB B1.046CH₂CH₃ H C—H CH C—CF₃ 2 DB B1.047 CH₂CH₃ H C—H CH C—Br 2 DB B1.048CH₂CH₃ H C—H CH C—Cl 2 DB B1.049 CH₂CH₃ H N N C—H 0 DB B1.050 CH₂CH₃ H NN C—CF₃ 0 DB B1.051 CH₂CH₃ H N N C—Br 0 DB B1.052 CH₂CH₃ H N N C—Cl 0 DBB1.053 CH₂CH₃ H N N C—H 1 DB B1.054 CH₂CH₃ H N N C—CF₃ 1 DB B1.055CH₂CH₃ H N N C—Br 1 DB B1.056 CH₂CH₃ H N N C—Cl 1 DB B1.057 CH₂CH₃ H N NC—H 2 DB B1.058 CH₂CH₃ H N N C—CF₃ 2 DB B1.059 CH₂CH₃ H N N C—Br 2 DBB1.060 CH₂CH₃ H N N C—Cl 2 DB B1.061 CH₃ H N C—H C—H 0 DB B1.062 CH₃ H NC—H C—CF₃ 0 DB B1.063 CH₃ H N C—H C—Br 0 DB B1.064 CH₃ H N C—H C—Cl 0 DBB1.065 CH₃ H N C—H C—H 1 DB B1.066 CH₃ H N C—H C—CF₃ 1 DB B1.067 CH₃ H NC—H C—Br 1 DB B1.068 CH₃ H N C—H C—Cl 1 DB B1.069 CH₃ H N C—H C—H 2 DBB1.070 CH₃ H N C—H C—CF₃ 2 DB B1.071 CH₃ H N C—H C—Br 2 DB B1.072 CH₃ HN C—H C—Cl 2 DB B1.073 CH₂CH₃ H N C—H C—H 0 DB B1.074 CH₂CH₃ H N C—HC—CF₃ 0 DB B1.075 CH₂CH₃ H N C—H C—Br 0 DB B1.076 CH₂CH₃ H N C—H C—Cl 0DB B1.077 CH₂CH₃ H N C—H C—H 1 DB B1.078 CH₂CH₃ H N C—H C—CF₃ 1 DBB1.079 CH₂CH₃ H N C—H C—Br 1 DB B1.080 CH₂CH₃ H N C—H C—Cl 1 DB B1.081CH₂CH₃ H N C—H C—H 2 DB B1.082 CH₂CH₃ H N C—H C—CF₃ 2 DB B1.083 CH₂CH₃ HN C—H C—Br 2 DB B1.084 CH₂CH₃ H N C—H C—Cl 2 DB B1.085 CH₃ H C—H C—H N 0DB B1.086 CH₃ H C—H C—H N 1 DB B1.087 CH₃ H C—H C—H N 2 DB B1.088 CH₂CH₃H C—H C—H N 0 DB B1.089 CH₂CH₃ H C—H C—H N 1 DB B1.090 CH₂CH₃ H C—H C—HN 2 DB B1.091 CH₃ H C—H N N 0 DB B1.092 CH₃ H C—H N N 1 DB B1.093 CH₃ HC—H N N 2 DB B1.094 CH₂CH₃ H C—H N N 0 DB B1.095 CH₂CH₃ H C—H N N 1 DBB1.096 CH₂CH₃ H C—H N N 2 DB B1.097 CH₃ H C—H N C—H 0 CH₂ B1.098 CH₃ HC—H N C—CF₃ 0 CH₂ B1.099 CH₃ H C—H N C—Br 0 CH₂ B1.100 CH₃ H C—H N C—Cl0 CH₂ B1.101 CH₃ H C—H N C—H 1 CH₂ B1.102 CH₃ H C—H N C—CF₃ 1 CH₂ B1.103CH₃ H C—H N C—Br 1 CH₂ B1.104 CH₃ H C—H N C—Cl 1 CH₂ B1.105 CH₃ H C—H NC—H 2 CH₂ B1.106 CH₃ H C—H N C—CF₃ 2 CH₂ B1.107 CH₃ H C—H N C—Br 2 CH₂B1.108 CH₃ H C—H N C—Cl 2 CH₂ B1.109 CH₂CH₃ H C—H C—H C—H 0 CH₂ B1.110CH₂CH₃ H C—H C—H C—CF₃ 0 CH₂ B1.111 CH₂CH₃ H C—H C—H C—Br 0 CH₂ B1.112CH₂CH₃ H C—H C—H C—Cl 0 CH₂ B1.113 CH₂CH₃ H C—H C—H C—H 1 CH₂ B1.114CH₂CH₃ H C—H C—H C—CF₃ 1 CH₂ B1.115 CH₂CH₃ H C—H C—H C—Br 1 CH₂ B1.116CH₂CH₃ H C—H C—H C—Cl 1 CH₂ B1.117 CH₂CH₃ H C—H C—H C—H 2 CH₂ B1.118CH₂CH₃ H C—H C—H C—CF₃ 2 CH₂ B1.119 CH₂CH₃ H C—H C—H C—Br 2 CH₂ B1.120CH₂CH₃ H C—H C—H C—Cl 2 CH₂ B1.121 CH₂CH₃ CH₃ C—H N C—H 0 DB B1.122CH₂CH₃ CH₃ C—H N C—CF₃ 0 DB B1.123 CH₂CH₃ CH₃ C—H N C—Br 0 DB B1.124CH₂CH₃ CH₃ C—H N C—Cl 0 DB B1.125 CH₂CH₃ CH₃ C—H N C—H 1 DB B1.126CH₂CH₃ CH₃ C—H N C—CF₃ 1 DB B1.127 CH₂CH₃ CH₃ C—H N C—Br 1 DB B1.128CH₂CH₃ CH₃ C—H N C—Cl 1 DB B1.129 CH₂CH₃ CH₃ C—H N C—H 2 DB B1.130CH₂CH₃ CH₃ C—H N C—CF₃ 2 DB B1.131 CH₂CH₃ CH₃ C—H N C—Br 2 DB B1.132CH₂CH₃ CH₃ C—H N C—Cl 2 DB

TABLE B Radicals of Formula B₂ B₂

Radical R₆ R₇ V₁ V₂ m B2.001 CH₃ H N C—H 0 B2.002 CH₃ H N C—CF₃ 0 B2.003CH₃ H N C—Br 0 B2.004 CH₃ H N C—Cl 0 B2.005 CH₃ H N C—H 1 B2.006 CH₃ H NC—CF₃ 1 B2.007 CH₃ H N C—Br 1 B2.008 CH₃ H N C—Cl 1 B2.009 CH₃ H N C—H 2B2.010 CH₃ H N C—CF₃ 2 B2.011 CH₃ H N C—Br 2 B2.012 CH₃ H N C—Cl 2B2.013 CH₃ H C—H C—H 0 B2.014 CH₃ H C—H C—CF₃ 0 B2.015 CH₃ H C—H C—Br 0B2.016 CH₃ H C—H C—Cl 0 B2.017 CH₃ H C—H C—H 1 B2.018 CH₃ H C—H C—CF₃ 1B2.019 CH₃ H C—H C—Br 1 B2.020 CH₃ H C—H C—Cl 1 B2.021 CH₃ H C—H C—H 2B2.022 CH₃ H C—H C—CF₃ 2 B2.023 CH₃ H C—H C—Br 2 B2.024 CH₃ H C—H C—Cl 2B2.025 CH₃ CH₃ C—H C—H 0 B2.026 CH₃ CH₃ C—H C—CF₃ 0 B2.027 CH₃ CH₃ C—HC—Br 0 B2.028 CH₃ CH₃ C—H C—Cl 0 B2.029 CH₃ CH₃ C—H C—H 1 B2.030 CH₃ CH₃C—H C—CF₃ 1 B2.031 CH₃ CH₃ C—H C—Br 1 B2.032 CH₃ CH₃ C—H C—Cl 1 B2.033CH₃ CH₃ C—H C—H 2 B2.034 CH₃ CH₃ C—H C—CF₃ 2 B2.035 CH₃ CH₃ C—H C—Br 2B2.036 CH₃ CH₃ C—H C—Cl 2

TABLE C Radicals of Formula B₃ B₃

Radical R₁₀ V₁ V₂ m B3.001 CH₃ N C—H 0 B3.002 CH₃ N C—CF₃ 0 B3.003 CH₃ NC—Br 0 B3.004 CH₃ N C—Cl 0 B3.005 CH₃ N C—H 2 B3.006 CH₃ N C—CF₃ 2B3.007 CH₃ N C—Br 2 B3.008 CH₃ N C—Cl 2 B3.009 CH₃ C—H C—H 0 B3.010 CH₃C—H C—CF₃ 0 B3.011 CH₃ C—H C—Br 0 B3.012 CH₃ C—H C—Cl 0 B3.013 CH₃ C—HC—H 2 B3.014 CH₃ C—H C—CF₃ 2 B3.015 CH₃ C—H C—Br 2 B3.016 CH₃ C—H C—Cl 2B3.017 CH₃ C—H C—H 0 B3.018 CH₃ C—H C—CF₃ 0 B3.019 CH₃ C—H C—Br 0 B3.020CH₃ C—H C—Cl 0 B3.021 CH₃ C—H C—H 2 B3.022 CH₃ C—H C—CF₃ 2 B3.023 CH₃C—H C—Br 2 B3.024 CH₃ C—H C—Cl 2

TABLE D Radicals of formula B₄ B₄

Radical R₁₂ V₁ V₂ B4.001 CH₃ N C—H B4.002 CH₃ N C—CF₃ B4.003 CH₃ N C—BrB4.004 CH₃ N C—Cl B4.005 CH₃ C—H C—H B4.006 CH₃ C—H C—CF₃ B4.007 CH₃ C—HC—Br B4.008 CH₃ C—H C—Cl

TABLE E Radicals of formula B₅ B₅

Radical V₁ V₂ m B5.001 N C—H 0 B5.002 N C—CF₃ 0 B5.003 N C—Br 0 B5.004 NC—Cl 0 B5.005 N C—H 1 B5.006 N C—CF₃ 1 B5.007 N C—Br 1 B5.008 N C—Cl 1B5.009 N C—H 2 B5.010 N C—CF₃ 2 B5.011 N C—Br 2 B5.012 N C—-Cl 2 B5.013C—H C—H 0 B5.014 C—H C—CF₃ 0 B5.015 C—H C—Br 0 B5.016 C—H C—Cl 0 B5.017C—H C—H 1 B5.018 C—H C—CF₃ 1 B5.019 C—H C—Br 1 B5.020 C—H C—Cl 1 B5.021C—H C—H 2 B5.022 C—H C—CF₃ 2 B5.023 C—H C—Br 2 B5.024 C—H C—Cl 2

TABLE F Radicals of formula B₆

Radical R₁₉ V₁ V₂ B6.001 C(CH₃)₃ N C—H B6.002 C(CH₃)₃ N C—CF₃ B6.003C(CH₃)₃ N C—Br B6.004 C(CH₃)₃ N C—Cl B6.005 C(CH₃)₃ C—H C—H B6.006C(CH₃)₃ C—H C—CF₃ B6.007 C(CH₃)₃ C—H C—Br B6.008 C(CH₃)₃ C—H C—Cl B6.009H N C—H B6.010 H N C—CF₃ B6.011 H N C—Br B6.012 H N C—Cl B6.013 H C—HC—H B6.014 H C—H C—CF₃ B6.015 H C—H C-Br B6.016 H C—H C—Cl

TABLE G Radicals of formula B₇ B₇

Radical R₃ V₄ V₃ m B7.001 CH₃ C—H C—H 0 B7.002 CH₃ C—H C—CF₃ 0 B7.003CH₃ C—H C—Br 0 B7.004 CH₃ C—H C—Cl 0 B7.005 CH₃ C—H C—H 1 B7.006 CH₃ C—HC—CF₃ 1 B7.007 CH₃ C—H C—Br 1 B7.008 CH₃ C—H C—Cl 1 B7.009 CH₃ C—H C—H 2B7.010 CH₃ C—H C—CF₃ 2 B7.011 CH₃ C—H C—Br 2 B7.012 CH₃ C−H C—Cl 2B7.013 CH₂CH₃ C—H C—H 0 B7.014 CH₂CH₃ C—H C—CF₃ 0 B7.015 CH₂CH₃ C—H C—Br0 B7.016 CH₂CH₃ C—H C—Cl 0 B7.017 CH₂CH₃ C—H C—H 1 B7.018 CH₂CH₃ C—HC—CF₃ 1 B7.019 CH₂CH₃ C—H C—Br 1 B7.020 CH₂CH₃ C—H C—Cl 1 B7.021 CH₂CH₃C—H C—H 2 B7.022 CH₂CH₃ C—H C—CF₃ 2 B7.023 CH₂CH₃ C—H C—Br 2 B7.024CH₂CH₃ C—H C—Cl 2 B7.025 CH₃ N C—H 0 B7.026 CH₃ N C—CF₃ 0 B7.027 CH₃ NC—Br 0 B7.028 CH₃ N C—Cl 0 B7.029 CH₃ N C—H 1 B7.030 CH₃ N C—CF₃ 1B7.031 CH₃ N C—Br 1 B7.032 CH₃ N C—Cl 1 B7.033 CH₃ N C—H 2 B7.034 CH₃ NC—CF₃ 2 B7.035 CH₃ N C—Br 2 B7.036 CH₃ N C—Cl 2 B7.037 CH₂CH₃ N C—H 0B7.038 CH₂CH₃ N C—CF₃ 0 B7.039 CH₂CH₃ N C—Br 0 B7.040 CH₂CH₃ N C—Cl 0B7.041 CH₂CH₃ N C—H 1 B7.042 CH₂CH₃ N C−CF₃ 1 B7.043 CH₂CH₃ N C—Br 1B7.044 CH₂CH₃ N C—Cl 1 B7.045 CH₂CH₃ N C—H 2 B7.046 CH₂CH₃ N C—CF₃ 2B7.047 CH₂CH₃ N C—Br 2 B7.048 CH₂CH₃ N C—Cl 2 B7.049 CH₃ N N 0 B7.050CH₃ N N 1 B7.051 CH₃ N N 2 B7.052 CH₂CH₃ N N 0 B7.053 CH₂CH₃ N N 1B7.054 CH₂CH₃ N N 2

TABLE H Radicals of formula B₈ B₈

Radical R₃ V₅ V₆ m B8.001 CH₃ C—H C—H 0 B8.002 CH₃ C—H C—H 1 B8.003 CH₃C—H C—H 2 B8.004 CH₂CH₃ C—H C—H 0 B8.005 CH₂CH₃ C—H C—H 1 B8.006 CH₂CH₃C—H C—H 2 B8.007 CH₃ C—H N 0 B8.008 CH₃ C—H N 1 B8.009 CH₃ C—H N 2B8.010 CH₂CH₃ C—H N 0 B8.011 CH₂CH₃ C—H N 1 B8.012 CH₂CH₃ C—H N 2

TABLE I Radicals of formula B₉ B₉

Radical R₃ V₈ V₇ m B9.001 CH₃ C—H C—H 0 B9.002 CH₃ C—H C—CF₃ 0 B9.003CH₃ C—H C—Br 0 B9.004 CH₃ C—H C—Cl 0 B9.005 CH₃ C—H C—H 1 B9.006 CH₃ C—HC—CF₃ 1 B9.007 CH₃ C—H C—Br 1 B9.008 CH₃ C—H C—Cl 1 B9.009 CH₃ C—H C—H 2B9.010 CH₃ C—H C—CF₃ 2 B9.011 CH₃ C—H C—Br 2 B9.012 CH₃ C—H C—Cl 2B9.013 CH₂CH₃ C—H C—H 0 B9.014 CH₂CH₃ C—H C—CF₃ 0 B9.015 CH₂CH₃ C—H C—Br0 B9.016 CH₂CH₃ C—H C—Cl 0 B9.017 CH₂CH₃ C—H C—H 1 B9.018 CH₂CH₃ C—HC—CF₃ 1 B9.019 CH₂CH₃ C—H C—Br 1 B9.020 CH₂CH₃ C—H C—Cl 1 B9.021 CH₂CH₃C—H C—H 2 B9.022 CH₂CH₃ C—H C—CF₃ 2 B9.023 CH₂CH₃ C—H C—Br 2 B9.024CH₂CH₃ C—H C—Cl 2 B9.025 CH₃ C—H N 0 B9.026 CH₃ C—H N 1 B9.027 CH₃ C—H N2 B9.028 CH₂CH₃ C—H N 0 B9.029 CH₂CH₃ C—H N 1 B9.030 CH₂CH₃ C—H N 2

TABLE J Radicals of formula B₁₀ B₁₀

Radical R₃ V₉ V₁₀ V₁₁ m B10.001 CH₂CH₃ C—H C—H C—H 0 B10.002 CH₂CH₃ C—HC—H C—H 1 B10.003 CH₂CH₃ C—H C—H C—H 2 B10.004 CH₂CH₃ N C—H C—H 0B10.005 CH₂CH₃ N C—H C—H 1 B10.006 CH₂CH₃ N C—H C—H 2 B10.007 CH₂CH₃ NC—H N 0 B10.008 CH₂CH₃ N C—H N 1 B10.009 CH₂CH₃ N C—H N 2 B10.010 CH₂CH₃N N N 0 B10.011 CH₂CH₃ N N N 1 B10.012 CH₂CH₃ N N N 2

TABLE K Radicals of formula B₁₁ B₁₁

Radical R₃ V₁ V₀ V₂ m B11.001 CH₃ C—H C—H C—H 0 B11.002 CH₃ C—H C—HC—CF₃ 0 B11.003 CH₃ C—H C—H C—Br 0 B11.004 CH₃ C—H C—H C—Cl 0 B11.005CH₃ C—H C—H C—H 1 B11.006 CH₃ C—H C—H C—CF₃ 1 B11.007 CH₃ C—H C—H C—Br 1B11.008 CH₃ C—H C—H C—Cl 1 B11.009 CH₃ C—H C—H C—H 2 B11.010 CH₃ C—H C—HC—CF₃ 2 B11.011 CH₃ C—H C—H C—Br 2 B11.012 CH₃ C—H C—H C—Cl 2 B11.013CH₃ N C—H C—H 0 B11.014 CH₃ N C—H C—CF₃ 0 B11.015 CH₃ N C—H C—Br 0B11.016 CH₃ N C—H C—Cl 0 B11.017 CH₃ N C—H C—H 1 B11.018 CH₃ N C—H C—CF₃1 B11.019 CH₃ N C—H C—Br 1 B11.020 CH₃ N C—H C—Cl 1 B11.021 CH₃ N C—HC—H 2 B11.022 CH₃ N C—H C—CF₃ 2 B11.023 CH₃ N C—H C—Br 2 B11.024 CH₃ NC—H C—Cl 2 B11.025 CH₂CH₃ C—H C—H C—H 0 B11.026 CH₂CH₃ C—H C—H C—CF₃ 0B11.027 CH₂CH₃ C—H C—H C—Br 0 B11.028 CH₂CH₃ C—H C—H C—Cl 0 B11.029CH₂CH₃ C—H C—H C—H 1 B11.030 CH₂CH₃ C—H C—H C—CF₃ 1 B11.031 CH₂CH₃ C—HC—H C—Br 1 B11.032 CH₂CH₃ C—H C—H C—Cl 1 B11.033 CH₂CH₃ C—H C—H C—H 2B11.034 CH₂CH₃ C—H C—H C—CF₃ 2 B11.035 CH₂CH₃ C—H C—H C—Br 2 B11.036CH₂CH₃ C—H C—H C—Cl 2 B11.037 CH₂CH₃ N C—H C—H 0 B11.038 CH₂CH₃ N C—HC—CF₃ 0 B11.039 CH₂CH₃ N C—H C—Br 0 B11.040 CH₂CH₃ N C—H C—Cl 0 B11.041CH₂CH₃ N C—H C—H 1 B11.042 CH₂CH₃ N C—H C—CF₃ 1 B11.043 CH₂CH₃ N C—HC—Br 1 B11.044 CH₂CH₃ N C—H C—Cl 1 B11.045 CH₂CH₃ N C—H C—H 2 B11.046CH₂CH₃ N C—H C—CF₃ 2 B11.047 CH₂CH₃ N C—H C—Br 2 B11.048 CH₂CH₃ N C—HC—Cl 2 B11.049 CH₂CH₃ C—H C—H N 0 B11.051 CH₂CH₃ C—H C—H N 1 B11.052CH₂CH₃ C—H C—H N 2 B11.053 CH₂CH₃ C—H N C—H 0 B11.054 CH₂CH₃ C—H N C—CF₃0 B11.055 CH₂CH₃ C—H N C—Br 0 B11.056 CH₂CH₃ C—H N C—Cl 0 B11.057 CH₂CH₃C—H N C—H 1 B11.058 CH₂CH₃ C—H N C—CF₃ 1 B11.059 CH₂CH₃ C—H N C—Br 1B11.060 CH₂CH₃ C—H N C—Cl 1 B11.061 CH₂CH₃ C—H N C—H 2 B11.062 CH₂CH₃C—H N C—CF₃ 2 B11.063 CH₂CH₃ C—H N C—Br 2 B11.064 CH₂CH₃ C—H N C—Cl 2

TABLE L Radicals of formula A₁ A₁

Radical R₁ R₂ G₁ G₂ G₃ A1.001 CH₃ H C—H C—H N—CH₃ A1.002 CF₃ H C—H C—HN—CH₃ A1.003 Cl H C—H C—H N—CH₃ A1.004 Br H C—H C—H N—CH₃ A1.005 CH₃ HC—H C—H O A1.006 CF₃ H C—H C—H O A1.007 Cl H C—H C—H O A1.008 Br H C—HC—H O A1.009 CH₃ H C—H C—H S A1.010 CF₃ H C—H C—H S A1.011 Cl H C—H C—HS A1.012 Br H C—H C—H S A1.013 CH₃ H C—H N N—CH₃ A1.014 CF₃ H C—H NN—CH₃ A1.015 Cl H C—H N N—CH₃ A1.016 Br H C—H N N—CH₃ A1.017 CH₃ H C—H NO A1.018 CF₃ H C—H N O A1.019 Cl H C—H N O A1.020 Br H C—H N O A1.021CH₃ H C—H N S A1.022 CF₃ H C—H N S A1.023 Cl H C—H N S A1.024 Br H C—H NS A1.025 CH₃ H N N N—CH₃ A1.026 CF₃ H N N N—CH₃ A1.027 Cl H N N N—CH₃A1.028 Br H N N N—CH₃ A1.029 CH₃ H N N O A1.030 CF₃ H N N O A1.031 Cl HN N O A1.032 Br H N N O A1.033 CH₃ H N N S A1.034 CF₃ H N N S A1.035 ClH N N S A1.036 Br H N N S

TABLE M Radicals of formula A₂ A₂

Radical R₁ R₂ G₁ G₂ G₅ A2.001 CH₃ H C—H C—H N A2.002 CF₃ H C—H C—H NA2.003 Cl H C—H C—H N A2.004 Br H C—H C—H N A2.005 CH₃ H C—H N N A2.006CF₃ H C—H N N A2.007 Cl H C—H N N A2.008 Br H C—H N N A2.009 CH₃ H N N NA2.010 CF₃ H N N N A2.011 Cl H N N N A2.012 Br H N N N A2.013 CH₃ H C—HC—H C—CH₃ A2.014 CF₃ H C—H C—H C—CH₃ A2.015 Cl H C—H C—H C—CH₃ A2.016 BrH C—H C—H C—CH₃ A2.017 CH₃ H C—H N C—CH₃ A2.018 CF₃ H C—H N C—CH₃ A2.019Cl H C—H N C—CH₃ A2.020 Br H C—H N C—CH₃ A2.021 CH₃ H N N C—CH₃ A2.022CF₃ H N N C—CH₃ A2.023 Cl H N N C—CH₃ A2.024 Br H N N C—CH₃

TABLE N Radicals of formula A₃ A₃

Radical R₁ R₂ G₁ G₂ G₄ A3.001 CH₃ H C—H C—H N A3.002 CF₃ H C—H C—H NA3.003 Cl H C—H C—H N A3.004 Br H C—H C—H N A3.005 CH₃ H C—H N N A3.006CF₃ H C—H N N A3.007 Cl H C—H N N A3.008 Br H C—H N N A3.009 CH₃ H N N NA3.010 CF₃ H N N N A3.011 Cl H N N N A3.012 Br H N N N A3.013 CH₃ H C—HC—H C—CH₃ A3.014 CF₃ H C—H C—H C—CH₃ A3.015 Cl H C—H C—H C—CH₃ A3.016 BrH C—H C—H C—CH₃ A3.017 CH₃ H C—H N C—CH₃ A3.018 CF₃ H C—H N C—CH₃ A3.019Cl H C—H N C—CH₃ A3.020 Br H C—H N C—CH₃ A3.021 CH₃ H N N C—CH₃ A3.022CF₃ H N N C—CH₃ A3.023 Cl H N N C—CH₃ A3.024 Br H N N C—CH₃

TABLE O Radicals of formula A₄ A₄

Radical J₂ J₃ G₁ G₂ G₃ A4.001 C—H O C—H C—H N—CH₃ A4.002 C—CF₃ O C—H C—HN—CH₃ A4.003 C—H S C—H C—H N—CH₃ A4.004 C—CF₃ S C—H C—H N—CH₃ A4.005 C—HO C—H N N—CH₃ A4.006 C—CF₃ O C—H N N—CH₃ A4.007 C—H S C—H N N—CH₃ A4.008C—CF₃ S C—H N N—CH₃

TABLE P Radicals of formula A₄ A₅

Radical R₁ R₂ G₁ G₂ G₅ G₄ A5.001 CH₃ H C—H C—H N N A5.002 CF₃ H C—H C—HN N A5.003 Cl H C—H C—H N N A5.004 Br H C—H C—H N N A5.005 CH₃ H C—H N NN A5.006 CF₃ H C—H N N N A5.007 Cl H C—H N N N A5.008 Br H C—H N N NA5.009 CH₃ H C—H C—H C—CH₃ N A5.010 CF₃ H C—H C—H C—CH₃ N A5.011 Cl HC—H C—H C—CH₃ N A5.012 Br H C—H C—H C—CH₃ N A5.013 CH₃ H C—H N C—CH₃ NA5.014 CF₃ H C—H N C—CH₃ N A5.015 Cl H C—H N C—CH₃ N A5.016 Br H C—H NC—CH₃ N

TABLE Q Radicals of formula A₆ A₆

Radical R₁ G₁ G₂ G₃ A6.001 CH₃ C—H C—H N—CH₃ A6.002 CF₃ C—H C—H N—CH₃A6.003 Cl C—H C—H N—CH₃ A6.004 Br C—H C—H N—CH₃ A6.005 CH₃ C—H C—H OA6.006 CF₃ C—H C—H O A6.007 Cl C—H C—H O A6.008 Br C—H C—H O A6.009 CH₃C—H C—H S A6.010 CF₃ C—H C—H S A6.011 Cl C—H C—H S A6.012 Br C—H C—H SA3.013 CH₃ C—H N N—CH₃ A6.014 CF₃ C—H N N—CH₃ A6.015 Cl C—H N N—CH₃A6.016 Br C—H N N—CH₃ A6.017 CH₃ C—H N O A6.018 CF₃ C—H N O A6.019 ClC—H N O A6.020 Br C—H N O A6.021 CH₃ C—H N S A6.022 CF₃ C—H N S A6.023Cl C—H N S A6.024 Br C—H N S

TABLE R Radicals of formula A_(7a) A_(7a)

Radical R₁ G₁ G₂ G₃ A7.001 CH₃ C—H C—H C—CH₃ A7.002 CF₃ C—H C—H C—CH₃A7.003 Cl C—H C—H C—CH₃ A7.004 Br C—H C—H C—CH₃ A7.005 CH₃ C—H C—H C—HA7.006 CF₃ C—H C—H C—H A7.007 Cl C—H C—H C—H A7.008 Br C—H C—H C—HA7.009 CH₃ C—H C—H N A7.010 CF₃ C—H C—H N A7.011 Cl C—H C—H N A7.012 BrC—H C—H N

TABLE S Radicals of formula A_(8a) A_(8a)

Radical R₁ G₁ G₂ G₄ A8.001 CH₃ C—H C—H C—H A8.002 CF₃ C—H C—H C—H A8.003Cl C—H C—H C—H A8.004 Br C—H C—H C—H A8.005 CH₃ C—H C—H C—CH₃ A8.006 CF₃C—H C—H C—CH₃ A8.007 Cl C—H C—H C—CH₃ A8.008 Br C—H C—H C—CH₃ A8.009 CH₃C—H C—H N A8.010 CF₃ C—H C—H N A8.011 Cl C—H C—H N A8.012 Br C—H C—H N

Table 1: This table discloses 66 compounds of the formula A1.014-B1wherein the radicals B1 are the radicals B1.049-B1.084, andB1.091-B1.120 shown in table A, and A1.014 is defined in Table L.

Table 2: This table discloses 66 compounds of the formula A1.018-B1wherein the radicals B1 are the radicals B1.049-B1.084, andB1.091-B1.120 shown in table A, and A1.018 is defined in Table L.

Table 3: This table discloses 66 compounds of the formula A1.022-B1wherein the radicals B1 are the radicals B1.049-B1.084, andB1.091-B1.120 shown in table A, and A1.022 is defined in Table L.

Table 4: This table discloses 36 compounds of the formula A1.014-B2wherein the radicals B2 are the radicals B2.001-B2.036 shown in table B,and A1.014 is defined in Table L.

Table 5: This table discloses 36 compounds of the formula A1.018-B2wherein the radicals B2 are the radicals B2.001-B2.036 shown in table B,and A1.018 is defined in Table L.

Table 6: This table discloses 36 compounds of the formula A1.022-B2wherein the radicals B2 are the radicals B2.001-B2.036 shown in table B,and A1.022 is defined in Table L.

Table 7: This table discloses 24 compounds of the formula A1.014-B3wherein the radicals B3 are the radicals B3.001-B3.024 shown in table C,and A1.014 is defined in Table L.

Table 8: This table discloses 24 compounds of the formula A1.018-B3wherein the radicals B3 are the radicals B3.001-B3.024 shown in table C,and A1.018 is defined in Table L.

Table 9: This table discloses 24 compounds of the formula A1.022-B3wherein the radicals B3 are the radicals B3.001-B3.024 shown in table C,and A1.022 is defined in Table L.

Table 10: This table discloses 8 compounds of the formula A1.014-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A1.014 is defined in Table L.

Table 11: This table discloses 8 compounds of the formula A1.018-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A1.018 is defined in Table L.

Table 12: This table discloses 8 compounds of the formula A1.022-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A1.022 is defined in Table L.

Table 13: This table discloses 24 compounds of the formula A1.014-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A1.014 is defined in Table L.

Table 14: This table discloses 24 compounds of the formula A1.018-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A1.018 is defined in Table L.

Table 15: This table discloses 24 compounds of the formula A1.022-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A1.022 is defined in Table L.

Table 16: This table discloses 16 compounds of the formula A1.014-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A1.014 is defined in Table L.

Table 17: This table discloses 16 compounds of the formula A1.018-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A1.018 is defined in Table L.

Table 18: This table discloses 16 compounds of the formula A1.022-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A1.022 is defined in Table L.

Table 19: This table discloses 54 compounds of the formula A1.014-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A1.014 is defined in Table L.

Table 20: This table discloses 54 compounds of the formula A1.018-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA1.018 is defined in Table L.

Table 21: This table discloses 54 compounds of the formula A1.022-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A1.022 is defined in Table L.

Table 22: This table discloses 12 compounds of the formula A1.014-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A1.014 is defined in Table L.

Table 23: This table discloses 12 compounds of the formula A1.018-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A1.018 is defined in Table L

Table 24: This table discloses 12 compounds of the formula A1.022-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A1.022 is defined in Table L

Table 25: This table discloses 30 compounds of the formula A1.014-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A1.014 is defined in Table L.

Table 26: This table discloses 30 compounds of the formula A1.018-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A1.018 is defined in Table L.

Table 27: This table discloses 30 compounds of the formula A1.022-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A1.0122 is defined in Table L.

Table 28: This table discloses 12 compounds of the formula A1.014-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A1.014 is defined in Table L.

Table 29: This table discloses 12 compounds of the formula A1.018-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A1.018 is defined in Table L.

Table 30: This table discloses 12 compounds of the formula A1.022-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A1.022 is defined in Table L.

Table 31: This table discloses 64 compounds of the formula A1.014-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A1.014 is defined in Table L.

Table 29: This table discloses 64 compounds of the formula A1.018-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A1.018 is defined in Table L.

Table 30: This table discloses 64 compounds of the formula A1.022-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A1.022 is defined in Table L.

Table 31: This table discloses 132 compounds of the formula A2.006-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A2.006 is defined in Table M.

Table 32: This table discloses 132 compounds of the formula A2.018-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A2.018 is defined in Table M.

Table 33: This table discloses 36 compounds of the formula A2.006-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A2.006 is defined in Table M.

Table 34: This table discloses 36 compounds of the formula A2.018-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A2.018 is defined in Table M.

Table 35: This table discloses 24 compounds of the formula A2.006-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A2.0006 is defined in Table M.

Table 36: This table discloses 24 compounds of the formula A2.018-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A2.018 is defined in Table M.

Table 37: This table discloses 8 compounds of the formula A2.006-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A2.006 is defined in Table M.

Table 38: This table discloses 8 compounds of the formula A2.018-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A2.018 is defined in Table M.

Table 39: This table discloses 24 compounds of the formula A2.006-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A2.006 is defined in Table M.

Table 40: This table discloses 24 compounds of the formula A2.018-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A2.018 is defined in Table M.

Table 42: This table discloses 16 compounds of the formula A2.006-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A2.006 is defined in Table M.

Table 43: This table discloses 16 compounds of the formula A2.018-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A2.018 is defined in Table M.

Table 44: This table discloses 54 compounds of the formula A2.006-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A2.0106 is defined in Table M.

Table 45: This table discloses 54 compounds of the formula A2.018-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA2.018 is defined in Table M.

Table 46: This table discloses 12 compounds of the formula A2.006-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A2.006 is defined in Table M.

Table 47: This table discloses 12 compounds of the formula A2.018-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A2.018 is defined in Table M.

Table 48: This table discloses 30 compounds of the formula A2.006-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A2.006 is defined in Table M.

Table 49: This table discloses 30 compounds of the formula A2.018-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A2.018 is defined in Table M.

Table 50: This table discloses 12 compounds of the formula A2.006-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A2.006 is defined in Table M.

Table 51: This table discloses 12 compounds of the formula A2.018-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A2.018 is defined in Table M.

Table 52: This table discloses 64 compounds of the formula A2.006-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A2.006 is defined in Table M.

Table 53: This table discloses 64 compounds of the formula A2.018-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A2.018 is defined in Table M.

Table 54: This table discloses 132 compounds of the formula A3.006-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A3.006 is defined in Table N.

Table 55: This table discloses 132 compounds of the formula A3.018-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A3.018 is defined in Table N.

Table 56: This table discloses 36 compounds of the formula A3.006-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A3.006 is defined in Table N.

Table 57: This table discloses 36 compounds of the formula A3.018-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A3.018 is defined in Table N.

Table 58: This table discloses 24 compounds of the formula A3.006-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A3.006 is defined in Table N.

Table 59: This table discloses 24 compounds of the formula A3.018-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A3.018 is defined in Table N.

Table 60: This table discloses 8 compounds of the formula A3.006-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A3.006 is defined in Table N.

Table 61: This table discloses 8 compounds of the formula A3.018-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A3.018 is defined in Table N.

Table 62: This table discloses 24 compounds of the formula A3.006-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A3.006 is defined in Table N.

Table 63: This table discloses 24 compounds of the formula A3.018-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A3.018 is defined in Table N.

Table 64: This table discloses 16 compounds of the formula A3.006-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A3.006 is defined in Table N.

Table 65: This table discloses 16 compounds of the formula A3.018-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A3.018 is defined in Table N.

Table 66: This table discloses 54 compounds of the formula A3.006-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A3.006 is defined in Table N.

Table 67: This table discloses 54 compounds of the formula A3.018-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA3.018 is defined in Table N.

Table 68: This table discloses 12 compounds of the formula A3.006-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A3.006 is defined in Table N.

Table 69: This table discloses 12 compounds of the formula A3.0018-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A3.018 is defined in Table N.

Table 70: This table discloses 30 compounds of the formula A3.006-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A3.006 is defined in Table N.

Table 71: This table discloses 30 compounds of the formula A3.018-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A3.018 is defined in Table N.

Table 72: This table discloses 12 compounds of the formula A3.006-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A3.006 is defined in Table N.

Table 73: This table discloses 12 compounds of the formula A3.018-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A3.018 is defined in Table N.

Table 74: This table discloses 64 compounds of the formula A3.006-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A3.006 is defined in Table N.

Table 75: This table discloses 64 compounds of the formula A3.018-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A3.018 is defined in Table N.

Table 76: This table discloses 132 compounds of the formula A4.006-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A4.006 is defined in Table O.

Table 77: This table discloses 132 compounds of the formula A4.008-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A4.008 is defined in Table O.

Table 78: This table discloses 36 compounds of the formula A4.006-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A4.006 is defined in Table O.

Table 79: This table discloses 36 compounds of the formula A4.008-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A4.008 is defined in Table O.

Table 80: This table discloses 24 compounds of the formula A4.006-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A4.006 is defined in Table O.

Table 81: This table discloses 24 compounds of the formula A4.008-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A4.008 is defined in Table O.

Table 82: This table discloses 8 compounds of the formula A4.006-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A4.006 is defined in Table O.

Table 83: This table discloses 8 compounds of the formula A4.008-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A4.008 is defined in Table O.

Table 84: This table discloses 24 compounds of the formula A4.006-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A4.006 is defined in Table O.

Table 85: This table discloses 24 compounds of the formula A4.008-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A4.008 is defined in Table O.

Table 86: This table discloses 16 compounds of the formula A4.006-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A4.006 is defined in Table O.

Table 87: This table discloses 16 compounds of the formula A4.008-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A4.008 is defined in Table O.

Table 88: This table discloses 54 compounds of the formula A4.006-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A4.006 is defined in Table O.

Table 89: This table discloses 54 compounds of the formula A4.008-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA4.008 is defined in Table O.

Table 90: This table discloses 12 compounds of the formula A4.006-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A4.006 is defined in Table O.

Table 91: This table discloses 12 compounds of the formula A4.008-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A4.008 is defined in Table O.

Table 92: This table discloses 30 compounds of the formula A4.006-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A4.006 is defined in Table O.

Table 93: This table discloses 30 compounds of the formula A4.008-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A4.008 is defined in Table O.

Table 94: This table discloses 12 compounds of the formula A4.006-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A4.006 is defined in Table O.

Table 95: This table discloses 12 compounds of the formula A4.008-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A4.008 is defined in Table O.

Table 96: This table discloses 64 compounds of the formula A4.006-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A4.006 is defined in Table O.

Table 97: This table discloses 64 compounds of the formula A4.008-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A3.008 is defined in Table O.

Table 98: This table discloses 132 compounds of the formula A5.006-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A5.006 is defined in Table P.

Table 99: This table discloses 36 compounds of the formula A5.006-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A5.006 is defined in Table P.

Table 100: This table discloses 24 compounds of the formula A5.006-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A5.006 is defined in Table P.

Table 101: This table discloses 8 compounds of the formula A5.006-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A4.006 is defined in Table P.

Table 102: This table discloses 24 compounds of the formula A5.006-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A5.006 is defined in Table P.

Table 103: This table discloses 16 compounds of the formula A5.006-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A5.006 is defined in Table P.

Table 104: This table discloses 54 compounds of the formula A5.006-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A5.006 is defined in Table P.

Table 105: This table discloses 12 compounds of the formula A5.006-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A5.006 is defined in Table P.

Table 106: This table discloses 30 compounds of the formula A5.006-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A5.006 is defined in Table P.

Table 107: This table discloses 12 compounds of the formula A5.006-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A5.006 is defined in Table P.

Table 108: This table discloses 64 compounds of the formula A5.006-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A5.006 is defined in Table P.

Table 109: This table discloses 132 compounds of the formula A6.002-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A6.002 is defined in Table Q.

Table 110: This table discloses 132 compounds of the formula A6.014-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A6.014 is defined in Table Q.

Table 111: This table discloses 36 compounds of the formula A6.002-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A6.002 is defined in Table Q.

Table 112: This table discloses 36 compounds of the formula A6.014-B2wherein the radicals B2 are the radicals B2.001-B2.0036 shown in tableB, and A6.014 is defined in Table Q.

Table 113: This table discloses 24 compounds of the formula A6.002-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A6.002 is defined in Table Q.

Table 114: This table discloses 24 compounds of the formula A6.014-B3wherein the radicals B3 are the radicals B3.001-B3.0024 shown in tableC, and A6.014 is defined in Table Q.

Table 115: This table discloses 8 compounds of the formula A6.002-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A6.002 is defined in Table Q.

Table 116: This table discloses 8 compounds of the formula A6.014-B4wherein the radicals B4 are the radicals B4.001-B4.008 shown in table D,and A6.014 is defined in Table Q.

Table 117: This table discloses 24 compounds of the formula A6.002-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A6.002 is defined in Table Q.

Table 118: This table discloses 24 compounds of the formula A6.014-B5wherein the radicals B5 are the radicals B5.001-B5.024 shown in table E,and A4.014 is defined in Table Q.

Table 119: This table discloses 16 compounds of the formula A6.002-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A6.002 is defined in Table Q.

Table 120: This table discloses 16 compounds of the formula A6.014-B6wherein the radicals B6 are the radicals B6.001-B6.016 shown in table F,and A6.014 is defined in Table Q.

Table 121: This table discloses 54 compounds of the formula A6.002-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A6.002 is defined in Table Q.

Table 122: This table discloses 54 compounds of the formula A6.014-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA6.014 is defined in Table Q.

Table 123: This table discloses 12 compounds of the formula A6.002-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A6.002 is defined in Table Q.

Table 124: This table discloses 12 compounds of the formula A6.0014-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A6.014 is defined in Table Q.

Table 125: This table discloses 30 compounds of the formula A6.002-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A6.002 is defined in Table Q.

Table 126: This table discloses 30 compounds of the formula A6.014-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A6.014 is defined in Table Q.

Table 127: This table discloses 12 compounds of the formula A6.002-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A6.002 is defined in Table Q.

Table 128: This table discloses 12 compounds of the formula A6.014-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A6.014 is defined in Table Q.

Table 129: This table discloses 64 compounds of the formula A6.002-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A6.002 is defined in Table Q.

Table 130: This table discloses 64 compounds of the formula A6.014-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A6.014 is defined in Table Q.

Table 131: This table discloses 132 compounds of the formula A7.002-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A7.002 is defined in Table R Table 132: This table discloses 132compounds of the formula A7.006-B1 wherein the radicals B1 are theradicals B1.001-B1.132 shown in table A, and A7.006 is defined in TableR.

Table 133: This table discloses 132 compounds of the formula A7.010-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A7.010 is defined in Table R.

Table 134: This table discloses 54 compounds of the formula A7.002-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A7.002 is defined in Table R.

Table 135: This table discloses 54 compounds of the formula A7.006-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA7.006 is defined in Table R.

Table 136: This table discloses 54 compounds of the formula A7.010-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA7.010 is defined in Table R.

Table 137: This table discloses 12 compounds of the formula A7.002-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A7.002 is defined in Table R.

Table 138: This table discloses 12 compounds of the formula A7.006-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A7.006 is defined in Table R.

Table 139: This table discloses 12 compounds of the formula A7.010-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A7.010 is defined in Table R.

Table 140: This table discloses 30 compounds of the formula A7.002-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A7.002 is defined in Table R.

Table 142: This table discloses 30 compounds of the formula A7.006-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A7.006 is defined in Table R.

Table 143: This table discloses 30 compounds of the formula A7.010-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A7.010 is defined in Table R.

Table 144: This table discloses 12 compounds of the formula A7.002-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A7.002 is defined in Table R.

Table 145: This table discloses 12 compounds of the formula A7.006-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A7.006 is defined in Table R.

Table 146: This table discloses 12 compounds of the formula A7.010-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A7.010 is defined in Table R.

Table 147: This table discloses 64 compounds of the formula A7.002-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A7.002 is defined in Table R.

Table 148: This table discloses 64 compounds of the formula A7.006-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A7.006 is defined in Table R.

Table 149: This table discloses 64 compounds of the formula A7.010-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A7.010 is defined in Table R.

Table 150: This table discloses 132 compounds of the formula A8.002-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A8.002 is defined in Table R

Table 151: This table discloses 132 compounds of the formula A8.006-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A8.006 is defined in Table S.

Table 152: This table discloses 132 compounds of the formula A8.010-B1wherein the radicals B1 are the radicals B1.001-B1.132 shown in table A,and A8.010 is defined in Table S.

Table 153: This table discloses 54 compounds of the formula A8.002-B7wherein the radicals B7 are the radicals B7.001-B7.054 shown in table G,and A8.002 is defined in Table S.

Table 154: This table discloses 54 compounds of the formula A8.006-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA8.006 is defined in Table R.

Table 155: This table discloses 54 compounds of the formula A8.010-B7wherein the B7 are the radicals B7.001-B7.054 shown in table G, andA8.010 is defined in Table R.

Table 156: This table discloses 12 compounds of the formula A8.002-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A8.002 is defined in Table S.

Table 157: This table discloses 12 compounds of the formula A8.006-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A8.006 is defined in Table S.

Table 158: This table discloses 12 compounds of the formula A8.010-B8wherein the radicals B8 are the radicals B8.001-B8.012 shown in table H,and A8.010 is defined in Table S.

Table 159: This table discloses 30 compounds of the formula A8.002-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A8.002 is defined in Table S.

Table 160: This table discloses 30 compounds of the formula A4.006-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A8.006 is defined in Table S.

Table 161: This table discloses 30 compounds of the formula A8.010-B9wherein the radicals B9 are the radicals B9.001-B9.030 shown in table I,and A8.010 is defined in Table S.

Table 162: This table discloses 12 compounds of the formula A8.002-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A8.002 is defined in Table S.

Table 164: This table discloses 12 compounds of the formula A8.006-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A8.006 is defined in Table S.

Table 165: This table discloses 12 compounds of the formula A8.010-B10wherein the radicals B10 are the radicals B10.001-B10.012 shown in tableJ, and A8.010 is defined in Table S.

Table 166: This table discloses 64 compounds of the formula A8.002-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A8.002 is defined in Table S.

Table 167: This table discloses 64 compounds of the formula A8.006-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A8.006 is defined in Table S.

Table 168: This table discloses 64 compounds of the formula A8.010-B11wherein the radicals B11 are the radicals B11.001-B11.064 shown in tableK, and A8.010 is defined in Table S.

TABLE T Physical-chemical data for compounds of formula I: Ret. EntryTime (M + H) Mpt. No. Compound (min) Measured Method ° C. T.1A1.014-B2.023 199-200 T.2 A1.014-B3.012 1.2 384/386 SQD13 169-170 T.3A1.014-B2.036 150-160 T.4 A2.014-B1.022 194-195 T.5 A1.014-B3.016197-198 T.6 A1.028-B1.022 140-141 T.7 A1.028-B1.013 122-123 T.8A1.014-B1.098 1.13 369 ZCQ13 T.9 A1.014-B1.106  101-103.5 T.10A2.018-B1.045 185-185 T.11 A2.022-B1.022 167-168 T.12 A1.014-B7.038161-163 T.13 A1.026-B1.022 190-192 T.14 A1.014-B7.014 79-80 T.15A1.014-B7.022 139-141 T.16 A1.026-B1.014 1.51 370 ZCQ13 T.17A1.014-B11.014 143-145 T.18 A1.014-B11.022 181-183 T.19 A1.028-B1.0141.11 418/420 ZQD13 159-162 T.20 A1.014-B7.038 1.27 413 ZQD13 206-209T.21 A1.014-B7.046 1.14 445 ZQD13 107-109 T.22 A1.026-B1.022 1.04 440SQD13 162-165 T.23 A6.02-B1.014 1.08 406 SQD13 137-140 T.24A1.014-B7.014 1.21 412 ZQD13 135-137 T.25 A1.014-B7.022 1.08 444 ZQD13152-154 T.26 A1.026-B1.014 1.13 408 ZQD13 172-175 T.27 A1.014-B8.10188-189 T.28 A1.014-B8.012 144-146 T.29 A6.02-B1.038 136-138 T.30A6.02-B9.014 82-84 T.31 A6.02-B7.037 167-169 T.32 A1.014-B11.014 122-124T.33 A6.015-B1.014 1.01 374/376 ZCQ13   156°-158° C. T.34 A1.014-B1.0501.12 408 SQD13 149-150 T.35 A1.014-B1.058 1.06 440 ZCQ13 172-174

TABLE U Physical-chemical data of especially preferred compounds offormula I and its intermediates: Entry COMPOUND RT [M + H] No. (IUPACname) (min) (measured) Method Mpt. ° C. U.12-(3-ethylsulfonyl-2-pyridyl)-7- 208-209 (trifluoromethyl)imidazo[1,2-b]pyridazine U.2 2-(3-ethylsulfonyl-2-pyridyl)-5- 0.82 357 SQD13(trifluoromethyl)-1H-imidazo[4,5- b]pyridine U.32-(3-Ethylsulfanyl-5-trifluoro-methyl- 1.15 461 SQD13 191-193pyridin-2-yl)-3,5-dimethyl-6- trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.4 2-(3-Ethylsulfanyl-pyridin-2-yl)-3,0.97 393 SQD13 129-131 5-dimethyl-6-trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.52-[3-ethylsulfanyl-5-(trifluoromethyl)-2- 1.09 393 SQD13 222-224pyridyl]-6-(trifluoromethyl)-3H- imidazo[4,5-c]pyridine U.62-[3-ethylsulfanyl-5-(trifluoromethyl)-2- 1.08 407 SQD13 119-121pyridyl]-1-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridine U.74-ethylsulfanyl-5-[3-methyl-6- 1.22 413 SQD13 100-102(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-2-(trifluoromethyl)thiazole U.8 4-ethylsulfonyl-5-[3-methyl-6- 1.02445 SQD13 172-174 (trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-2-(trifluoromethyl)thiazole U.9 6-(3-ethylsulfonyl-2-pyridyl)-3-199-201 (trifluoromethyl)imidazo[1,2- b][1,2,4]triazine U.103-methyl-2-[3-(oxiran-2- 1.03 467 ZQD13ylmethylsulfonyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5- b]pyridine U.113-methyl-2-[3-(oxetan-3- 1.01 481 ZQD13ylmethylsulfonyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5- b]pyridine U.123-methyl-2-[3-(tetrahydrofuran-3- 1.05 495 ZQD13ylmethylsulfonyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5- b]pyridine U.133-methyl-2-[3-(tetrahydrofuran-2- 1.11 495 ZQD13ylmethylsulfonyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[4,5- b]pyridine U.142-[6-chloro-3-ethylsulfonyl-5- 1.14 473/475 ZQD13(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.155-ethylsulfonyl-6-[3-methyl-6- 0.91 455 ZQD13(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-(trifluoromethyl)pyridin-2-ol U.162-(3-ethylsulfanyl-5-methyl-2-pyridyl)-3- 1.17 407 ZQD13 141-143methyl-5-(trifluoromethyl)imidazo[4,5- b]pyridine U.172-[3-cyclobutylsulfonyl-5- 1.12 465 SQD13 149-150(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.183-methyl-2-[3-pyrimidin-2-ylsulfonyl-5- 1.64   489.00 ZQ2000(trifluoromethyl)-2-pyridyl]-6- (trifluoromethyl)imidazo[4,5-b]pyridineU.19 3-methyl-2-[3-(4-pyridylsulfonyl)-5- 1.50 488 ZQ2000(trifluoromethyl)-2-pyridyl]-6- (trifluoromethyl)imidazo[4,5-b]pyridineU.20 2-[3-cyclohexylsulfonyl-5- 2.02 493 ZQ2000(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.21 2-[3-cyclopentylsulfonyl-5-1.91 479 ZQ2000 (trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.22 2-[[2-[3-methyl-6- 1.66 495ZQ2000 (trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-5-(trifluoromethyl)-3-pyridyl]sulfonyl]- 1,3,4-thiadiazole U.233-methyl-2-[3-(2-thienylsulfonyl)-5- 1.76 493 ZQ2000(trifluoromethyl)-2-pyridyl]-6- (trifluoromethyl)imidazo[4,5-b]pyridineU.24 3-methyl-2-[3-(2-thienylsulfinyl)-5- 1.94 477 ZQ2000(trifluoromethyl)-2-pyridyl]-6- (trifluoromethyl)imidazo[4,5-b]pyridineU.25 2-[3-(cyclobutylmethylsulfonyl)-5- 1.18 479 ZQD13 110-111(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.262-[3-[2-(1,3-dioxan-2-yl)ethylsulfanyl]-5- 1.16 493 ZQD13 100-101(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.272-[3-[2-(1,3-dioxolan-2-yl)ethylsulfanyl]- 1.1 465 ZQD13 104-1055-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.282-[3-[2-(1,3-dioxan-2-yl)ethylsulfonyl]-5- 144-145(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.292-[3-[2-(1,3-dioxolan-2-yl)ethylsulfonyl]- 140-1415-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.302-[3-(1,3-dioxolan-2-ylmethylsulfonyl)-5- 149-150(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.312-[3-ethylsulfanyl-5-(trifluoromethyl)-2- 124-126pyridyl]-6-(trifluoromethyl)pyrazolo[1,5- a]pyrimidine U.322-[3-ethylsulfonyl-5-(trifluoromethyl)-2- 189-191pyridyl]-6-(trifluoromethyl)pyrazolo[1,5- a]pyrimidine U.334-bromo-5-[3-methyl-6- 1.03 431/433 ZQD13(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole U.34 4-ethylsulfanyl-5-[3-methyl-6-92-94 (trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-(trifluoromethyl)thiazole U.35 2-[3-ethylsulfanyl-6- 206-208(trifluoromethyl)pyrazin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.36 2-[3-ethylsulfonyl-6-214-216 (trifluoromethyl)pyrazin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.372-[5-(difluoromethoxy)-3-ethylsulfanyl- 82-83 2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.382-[5-(difluoromethoxy)-3-ethylsulfonyl- 115-117 2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.39 2-[2-ethylsulfanyl-4-120-122 (trifluoromethyl)phenyl]-1-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine U.40 2-[2-ethylsulfonyl-4-237-239 (trifluoromethyl)phenyl]-1-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine U.415-bromo-2-[3-ethylsulfonyl-5- 94-97(trifluoromethyl)-2-pyridyl]-1-methyl- imidazo[4,5-b]pyridine U.422-[3-ethylsulfonyl-5-(trifluoromethyl)-2- 202-204 pyridyl]-1-methyl-5-(trifluoromethyl)imidazo[4,5-b]pyridine U.435-bromo-2-(3-ethylsulfonyl-2-pyridyl)-1- 183-186methyl-imidazo[4,5-b]pyridine U.442-[3-ethylsulfonyl-5-(trifluoromethyl)-2- 191-192pyridyl]-7-(trifluoromethyl)imidazo[1,2- a]pyridine U.453-chloro-2-[3-ethylsulfonyl-5- 195-197 (trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine U.463-bromo-2-[3-ethylsulfonyl-5- 202-204 (trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine U.473-bromo-2-[3-ethylsulfonyl-5- 180-182 (trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2- c]pyrimidine U.482-[3-(1,3-dioxan-2-ylmethylsulfonyl)-5- 1.09 511 SQD13(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.493-bromo-2-(3-ethylsulfonyl-2-pyridyl)-7- 174-175(trifluoromethyl)imidazo[1,2- c]pyrimidine U.502-[3-(4-methoxyphenyl)sulfinyl-5- 156-158(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine U.513-bromo-2-[3-ethylsulfonyl-5- 223-224 (trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl)imidazo[1,2-a]pyrazine U.526-bromo-2-[3-ethylsulfonyl-5- 221-223(trifluoromethyl)-2-pyridyl]imidazo[1,2- a]pyrazine U.533-bromo-2-(3-ethylsulfonyl-2-pyridyl)-6- 200-212(trifluoromethyl)imidazo[1,2-a]pyrazine U.546-bromo-2-(3-ethylsulfonyl-2- 219-220 pyridyl)imidazo[1,2-a]pyrazineU.55 2-(3-Ethylsulfanyl-5-trifluoromethyl- 164-166thiophen-2-yl)-3,5-dimethyl-6- trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.562-(5-Ethylsulfanyl-thiazol-4-yl)-3, 200-2025-dimethyl-6-trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.572-[2-ethylsulfanyl-6-(trifluoromethyl)-3- 115-117 pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine U.582-[2-ethylsulfanyl-6-(trifluoromethyl)-3- 117-119pyridyl]-7-(trifluoromethyl)imidazo[1,2- a]pyridine U.592-[5-(difluoromethoxy)-3-ethylsulfanyl- 146-148 2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine U.603-ethylsulfanyl-4-[3-methyl-6- 163-165(trifluoromethyl)imidazo[4,5-b]pyridin-2- yl]isothiazole U.612-[3-ethylsulfanyl-5-(trifluoromethyl)-2-  98-100thienyl]-7-(trifluoromethyl)imidazo[1,2- a]pyridine U.624-bromo-2-(trifluoromethyl)-5-[7- 152-154(trifluoromethyl)imidazo[1,2-a]pyridin-2- yl]thiazole U.632-(4-Ethylsulfanyl-2-trifluoromethyl- 196-198thiazol-5-yl)-3,5-dimethyl-6- trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.642-(2-Ethylsulfanyl-6-trifluoromethyl- 154-156pyridin-3-yl)-3,5-dimethyl-6- trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.652-[3-ethylsulfonyl-5-(trifluoromethyl)-2- 1.56 439 ZCQ13pyridyl]-3-methyl-7- (trifluoromethyl)imidazo[1,2- a]pyrimidine U.664-ethylsulfanyl-2-(trifluoromethyl)-5- 1.25 398 SQD13 115-117[7-(trifluoromethyl)imidazo[1,2- a]pyridin-2-yl]thiazole U.673-bromo-2-[3-ethylsulfonyl-5- 1.13 507/509 SQD13 176-178(trifluoromethyl)-2-thienyl]-7- (trifluoromethyl)imidazo[1,2- a]pyridineU.68 2-[3-ethylsulfanyl-5-(trifluoromethyl)- 1.22 398 SQD13 94-962-thienyl]-7-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridine U.694-bromo-2-(trifluoromethyl)-5-[7- 1.15 417/419 SQD13 90-91(trifluoromethyl)-[1,2,4]triazolo[1,5- a]pyridin-2-yl]thiazole U.704-ethylsulfanyl-2-(trifluoromethyl)-5- 1.24 399 SQD13 102-103[7-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridin-2- yl]thiazole U.712-[3-ethylsulfanyl-5-(trifluoromethyl)- 1.22 398 SQD13 121-1232-thienyl]-6-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridine U.722-(2-Ethylsulfanyl-5-trifluoromethyl- 1.18 466 SQD13 121-123thiophen-3-yl)-3,5-dimethyl-6- trifluoromethyl-3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.732-(2-Ethylsulfanyl-4-trifluoromethyl- 1.13 460 SQD13 201-203phenyl)-3,5-dimethyl-6-trifluoromethyl- 3,5-dihydro-diimidazo[4,5-b;4′,5′-e]pyridine U.74 2-[2-ethylsulfanyl-5-(trifluoromethyl)- 1.12 412SQD13 148-150 3-thienyl]-3-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridine

Preference is given to a group of compounds of formula I defined asembodiments (1) to (7) which are illustrated below:

An especially preferred group of compounds of formula I according to theinvention is defined as embodiment (1) and comprises combinations of

(1): Radical A2 with radicals B selected from B7, B9 and E11;wherein A2 is preferably represented by the radical A2.1

wherein R₄₀ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl; G₂₁ is nitrogen, CH, C—C₁-C₆ alkyl,C—C₁-C₆haloalkyl, C-halogen, C—CN, C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl,C—SO₂—C₁-C₄alkyl, C—S-phenyl, C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; andG₅₁ is nitrogen, CH, C—C₁-C₆ alkyl, C—C₁-C₆haloalkyl, C-halogen, C—CN,C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl, C—SO₂—C₁-C₄alkyl, C—S-phenyl,C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; and the radicals B7, B9 and E11are preferably represented by the radicals selected from B7.1, B9.1 andB11.1

wherein m is 0, 1 or 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2;R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.

Especially preferred compounds according to embodiment (1) arerepresented by embodiment (1.1), wherein

(1.1) in the radical A2.1

R₄₀ is C₁-C₄haloalkyl, in particular trifluoromethyl;G₂₁ is nitrogen or CH; andG₅₁ is nitrogen or C—C₁-C₅ alkyl, in particular nitrogen or C-methyl;and in the radicals B7.1, B9.1 and B11.1

m is 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, preferably ethyl; andR₄₂ is C₁-C₄haloalkyl, preferably trifluoromethyl;

m is 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, preferably ethyl; andR₄₄ is C₁-C₄haloalkyl, preferably trifluoromethyl;

m is 2;R₄₅ is C₁-C₄alkyl, preferably ethyl; andR₄₆ is C₁-C₄haloalkyl, preferably trifluoromethyl.

A further especially preferred group of compounds of formula I accordingto the invention is defined as embodiment (2) and comprises combinationsof

(2): Radical A3 with radicals B selected from B7, B9 and B11;wherein A3 is preferably represented by the radical A3.1

wherein R₄₇ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl;G₄₁ is nitrogen, CH, C—C₁-C₆ alkyl, C—C₁-C₆haloalkyl, C-halogen, C—CN,C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl, C—SO₂—C₁-C₄alkyl, C—S-phenyl,C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; andG₂₂ is nitrogen, CH, C—C₁-C₆ alkyl, C—C₁-C₆haloalkyl, C-halogen, C—CN,C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl, C—SO₂—C₁-C₄alkyl, C—S-phenyl,C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; and the radicals B7, B9 and B11are preferably represented by the radicals selected from B7.1, B9.1 andB11.1

wherein m is 0, 1 or 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2;R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.

Especially preferred compounds according to embodiment (2) arerepresented by embodiment (2.1), wherein

(2.1) in the radical A3.1

R₄₇ is C₁-C₄haloalkyl, in particular trifluoromethyl;G₂₂ is nitrogen or CH; andG₄₁ is nitrogen, or C—C₁-C₅ alkyl, in particular nitrogen or C-methyl;and in the radicals B7.1, B9.1 and B11.1

m is 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, preferably ethyl; andR₄₂ is C₁-C₄haloalkyl, preferably trifluoromethyl;

m is 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, preferably ethyl; andR₄₄ is C₁-C₄haloalkyl, preferably trifluoromethyl;

m is 2;R₄₅ is C₁-C₄alkyl, preferably ethyl; andR₄₆ is C₁-C₄haloalkyl, preferably trifluoromethyl.

A further especially preferred group of compounds of formula I accordingto the invention is defined as embodiment (3) and comprises combinationsof

(3): Radical A4 with radical B1,wherein A4 is preferably represented by the radical A4.1

wherein R₄₈ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl; J₃ is sulfur oxygen or N-methyl; andR₄₉ is hydrogen, C₁-C₆ alkyl, C₁-C₆haloalkyl, halogen, CN, O—C₁-C₄alkyl,S—C₁-C₄alkyl, SO₂—C₁-C₄alkyl, S-phenyl, SO₂-phenyl orSO₂—C₁-C₄halolakyl;and the radical 1 is

wherein m is 0, 1 or 2;R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₅₀ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

Preferred compounds according to embodiment (3) are also represented byembodiment (3.1), wherein

(3.1) in the radical A4.1

R₄₈ is C₁-C₄haloalkyl, in particular trifluoromethyl;J₃ is oxygen, sulphur or N-methyl; andR₄₉ is hydrogen or C₁-C₆ alkyl, in particular hydrogen or methyl;and the radicals B1, B7, B9 and B11 are preferably represented by theradicals selected from B1.1, B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2;R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₅₀ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2;R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.

Further especially preferred compounds according to embodiment (3) arerepresented by embodiment (3.2), wherein (3.2) in the radical A4.1

R₄₈ is C₁-C₄haloalkyl, in particular trifluoromethyl;J₃ is oxygen, sulphur or N-methyl; andR₄₉ is hydrogen or C₁-C₆ alkyl, in particular hydrogen or methyl;and in the radical B1.1

m is 2;V11 is nitrogen or methine;R₅₁ is C₁-C₄alkyl, preferably ethyl; andR₅₀ is hydrogen or C₁-C₄haloalkyl, preferably hydrogen ortrifluoromethyl.

A further especially preferred group of compounds of formula I accordingto the invention is defined as embodiment (4) and comprises combinationsof

(4): Radical A5 with radicals B selected from 1, B7, B9 and E11;wherein A5 is preferably represented by the radical A5.1

whereinG₅₅ is nitrogen or C—R₅₃;R₅₃ is C₁-C₄alkyl;G₂₅ is nitrogen or methine; andR₅₂ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl;and the radicals B1, B7, B9 and B11 are preferably represented by theradicals selected from B1.1, B7.1, B9.1 and E11.1

wherein m is 0, 1 or 2;R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₅₀ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2;R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.

Especially preferred compounds according to embodiment (4) arerepresented by embodiment (4.1), wherein

(4.1) in the radical A5.1

R₅₂ is C₁-C₄haloalkyl, in particular trifluoromethyl;G₅₅ is nitrogen or C—C₁-C₄alkyl, preferably nitrogen or methyl; andG₂₅ is nitrogen or methine;and in the radical B1.1

m is 2;V₁₁ is nitrogen or methine;R₅₁ is C₁-C₄alkyl, preferably ethyl; andR₅₀ is hydrogen or C₁-C₄haloalkyl, preferably hydrogen ortrifluoromethyl; in the radical B7.1

m is 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, preferably ethyl; andR₄₂ is C₁-C₄haloalkyl, preferably trifluoromethyl;in the radical B9.1

m is 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, preferably ethyl; andR₄₄ is C₁-C₄haloalkyl, preferably trifluoromethyl;and in the radical B11.1

m is 2;R₄₅ is C₁-C₄alkyl, preferably ethyl; andR₄₆ is C₁-C₄haloalkyl, preferably trifluoromethyl.

A further especially preferred group of compounds of formula I accordingto the invention is defined as embodiment (5) and comprises combinationsof

(5): Radical A6 with radicals B selected from 1, B7, B9 and B11;wherein A6 is preferably represented by the radical A6.1

whereinG₃₆ is N—R₅₅, oxygen or sulfur;R₅₅ is C₁-C₄alkyl;G₂₆ is nitrogen or methine; andR₅₄ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl;and the radicals B1, B7, B9 and B11 are preferably represented by theradicals selected from B1.1, B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2;R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₅₀ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;is nitrogen or methine;R₄₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2;R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.

Especially preferred compounds according to embodiment (5) arerepresented by embodiment (5.1), wherein

(5.1) in the radical A6.1

R₅₄ is C₁-C₄haloalkyl, in particular trifluoromethyl;G₃₆ is N—C₁-C₄alkyl, oxygen or sulfur; preferably N—CH₃, oxygen orsulfur; andG₂₆ is nitrogen or methine;and in the radical B1.1

m is 2;V₁₁ is nitrogen or methine;R₅₁ is C₁-C₄alkyl, preferably ethyl; andR₅₀ is hydrogen or C₁-C₄haloalkyl, preferably hydrogen ortrifluoromethyl; in the radical B7.1

m is 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, preferably ethyl; andR₄₂ is C₁-C₄haloalkyl, preferably trifluoromethyl;in the radical B9.1

m is 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, preferably ethyl; andR₄₄ is C₁-C₄haloalkyl, preferably trifluoromethyl;and in the radical B11.1

m is 2;R₄₅ is C₁-C₄alkyl, preferably ethyl; andR₄₆ is C₁-C₄haloalkyl, preferably trifluoromethyl.

A further especially preferred group of compounds of formula I accordingto the invention is defined as embodiment (6) and comprises combinationsof

(6): Radical A7 with radicals B selected from 1, B7, B9 and E11;wherein A7 is preferably represented by the radical A7.1

whereinG₅₇ is nitrogen or C—R₅₇;R₅₇ is hydrogen or C₁-C₄alkyl; andR₅₆ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl;and the radicals B1, B7, B9 and B11 are preferably represented by theradicals selected from B1.1, B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2;R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₅₀ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₂ is nitrogen methine;R₄₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2;R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.

Especially preferred compounds according to embodiment (6) arerepresented by embodiment (6.1), wherein

(6.1) in the radical A7.1

R₅₆ is C₁-C₄haloalkyl, in particular trifluoromethyl; andG₅₇ is nitrogen, C—H or C—C₁-C₄alkyl; preferably nitrogen, C—H or C—CH₃;and in the radical B1.1

m is 2;V₁₁ is nitrogen or methine;R₅₁ is C₁-C₄alkyl, preferably ethyl; andR₅₀ is hydrogen or C₁-C₄haloalkyl, preferably hydrogen ortrifluoromethyl; in the radical B7.1

m is 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, preferably ethyl; andR₄₂ is C₁-C₄haloalkyl, preferably trifluoromethyl;in the radical B9.1

m is 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, preferably ethyl; andR₄₄ is C₁-C₄haloalkyl, preferably trifluoromethyl;and in the radical B11.1

m is 2;R₄₅ is C₁-C₄alkyl, preferably ethyl; andR₄₆ is C₁-C₄haloalkyl, preferably trifluoromethyl.

A further especially preferred group of compounds of formula I accordingto the invention is defined as embodiment (7) and comprises combinationsof

(7): Radical A8 with radicals B selected from 1, B7, B9 and E11;wherein A8 is preferably represented by the radical A8.1

whereinG₄₈ is nitrogen or C—R₅₉;R₅₉ is hydrogen or C₁-C₄alkyl; andR₅₈ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl;and the radicals B1, B7, B9 and B11 are preferably represented by theradicals selected from B1.1, B7.1, B9.1 and E11.1

wherein m is 0, 1 or 2;R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₅₀ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2;R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₆ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.

Especially preferred compounds according to embodiment (7) arerepresented by embodiment (7.1), wherein

(7.1) in the radical A8.1

R₅₈ is C₁-C₄haloalkyl, in particular trifluoromethyl; andG₄₈ is nitrogen, C—H or C—C₁-C₄alkyl; preferably nitrogen, C—H or C—CH₃;and in the radical B1.1

m is 2;V₁₁ is nitrogen or methine;R₅₁ is C₁-C₄alkyl, preferably ethyl; andR₅₀ is hydrogen or C₁-C₄haloalkyl, preferably hydrogen ortrifluoromethyl; in the radical B7.1

m is 2;V₈₂ is nitrogen or methine;R₄₁ is C₁-C₄alkyl, preferably ethyl; andR₄₂ is C₁-C₄haloalkyl, preferably trifluoromethyl;in the radical B9.1

m is 2;V₈₁ is nitrogen or methine,R₄₃ is C₁-C₄alkyl, preferably ethyl; andR₄₄ is C₁-C₄haloalkyl, preferably trifluoromethyl;and in the radical B11.1

m is 2;R₄₅ is C₁-C₄alkyl, preferably ethyl; andR₄₆ is C₁-C₄haloalkyl, preferably trifluoromethyl.

Especially preferred compounds of formula I of the invention are listedin the following tables V1 to V26. The tables V1 to V26 representfurther embodiments of the invention: In these tables Et is CH₂CH₃, Meis CH₃, NMe is N—CH3, CMe is C-Me etc.

TABLE V1 Compounds of the formula A2.1-B7.1: (A2.1-B7.1)

Ret. Time No. R₄₀ R₄₁ R₄₂ m G₂₁ G₅₁ V₈₂ Mpt. ° C. (mins) (M + H) MethodV1.01 CF₃ Et CF₃ 2 CH N CH 160-161 V1.02 CF₃ Et CF₃ 2 N N CH 156-159V1.03 CF₃ Et CF₃ 2 CH CMe CH V1.04 CF₃ Et CF₃ 2 N CMe CH V1.05 CF₃ EtCF₃ 2 CH CH CH V1.06 CF₃ Et CF₃ 2 N CH CH 187-190 V1.07 CF₃ Et CF₃ 2 CHCH N V1.08 CF₃ Et H 2 CH CH N

TABLE V2 Compounds of the formula A2.1-B9.1: (A2.1-B9.1)

Ret. time No. R₄₀ R₄₃ R₄₄ V₈₁ m G₂₁ G₅₁ Mpt. ° C. (mins) (M + H) MethodV2.01 CF₃ Et CF₃ CH 2 CH N 136-138 1.08 430 SQD13 V2.02 CF₃ Et CF₃ CH 2N N 109-111 V2.03 CF₃ Et CF₃ CH 2 CH CMe 190-192 1.08 443 SQD13 V2.04CF₃ Et CF₃ CH 2 N CMe 92-94 1.11 444 SQD13 V2.05 CF₃ Et CF₃ CH 2 CH CH174-176 1.13 429 SQD13 V2.06 CF₃ Et CF₃ CH 2 N CH 209-211 1.11 430 SQD13V2.07 CF₃ Et CF₃ N 2 CH N 129-130 1.10 431 SQD13 V2.08 CF₃ Et CF₃ N 2 NN 119-120 V2.09 CF₃ Et CF₃ N 2 CH CMe V2.10 CF₃ Et CF₃ N 2 N CMe V2.11CF₃ Et CF₃ N 2 CH CH 126-128 V2.12 CF₃ Et CF₃ N 2 N CH 192-194

TABLE V3 Compounds of the formula A2.1-B11.1: (A2.1-B11.1)

Ret. time No. R₄₀ R₄₅ R₄₆ m G₂₁ G₅₁ Mpt. ° C. (mins) (M + H) MethodV3.01 CF₃ Et CF₃ 2 CH N 133-134 0.95 425 SQD13 V3.02 CF₃ Et CF₃ 2 N N158-159 0.93 426 SQD13 V3.03 CF₃ Et CF₃ 2 CH CMe V3.04 CF₃ Et CF₃ 2 NCMe 106-108 1.01 439 SQD13 V3.05 CF₃ Et CF₃ 2 CH CH 188-190 1.07 424SQD13 V3.06 CF₃ Et CF₃ 2 N CH 135-137 1.03 425 SQD13

TABLE V4 Compounds of the formula A3.1-B7.1: (A3.1-B7.1)

Ret. time No. R₄₇ R₄₁ R₄₂ m G₂₂ G₄₁ V₈₂ Mpt. ° C. (mins) (M + H) MethodV4.01 CF₃ Et CF₃ 2 CH N CH 198-199 V4.02 CF₃ Et CF₃ 2 N N CH 195-197V4.03 CF₃ Et CF₃ 2 CH CMe CH V4.04 CF₃ Et CF₃ 2 N CMe CH V4.05 CF₃ EtCF₃ 2 CH CH CH V4.06 CF₃ Et CF₃ 2 N CH CH

TABLE V5 Compounds of the formula A3.1-B9.1: (A3.1-B9.1)

Ret. time No. R₄₇ R₄₃ R₄₄ m G₂₂ G₄₁ V₈₁ Mpt. ° C. (mins) (M + H) MethodV5.01  CF₃ Et CF₃ 2 CH N CH 147-149 1.08 430 SQD13 V5.02  CF₃ Et CF₃ 2 NN CH 156-158 V5.03  CF₃ Et CF₃ 2 CH CMe CH V5.04  CF₃ Et CF₃ 2 N CMe CHV5.05  CF₃ Et CF₃ 2 CH CH CH V5.06  CF₃ Et CF₃ 2 N CH CH V5.07  CF₃ EtCF₃ 2 CH N N 127-128 1.0 431 SQD13 V5.08  CF₃ Et CF₃ 2 N N N 130-131V5.09  CF₃ Et CF₃ 2 CH CMe N V5.010 CF₃ Et CF₃ 2 N CMe N V5.011 CF₃ EtCF₃ 2 CH CH N V5.012 CF₃ Et CF₃ 2 N CH N

TABLE V6 Compounds of the formula A3.1-B11.1: (A3.1-B11.1)

Ret. time No. R₄₇ R₄₅ R₄₆ m G₂₂ G₄₁ Mpt. ° C. (mins) (M + H) MethodV6.01 CF₃ Et CF₃ 2 CH N 155-156 0.95 425 SQD13 V6.02 CF₃ Et CF₃ 2 N N201-203 0.89 426 SQD13 V6.03 CF₃ Et CF₃ 2 CH CMe V6.04 CF₃ Et CF₃ 2 NCMe V6.05 CF₃ Et CF₃ 2 CH CH V6.06 CF₃ Et CF₃ 2 N CH

TABLE V7 Compounds of the formula A4.1-B1.1: (A4.1-B1.1)

Ret. time No. R₄₈ R₅₁ R₅₀ m J₃ R₄₉ V₁₁ Mpt. ° C. (mins) (M + H) MethodV7.01 CF₃ Et CF₃ 2 O Me N V7.02 CF₃ Et CF₃ 2 S Me N V7.03 CF₃ Et CF₃ 2 OMe CH V7.04 CF₃ Et CF₃ 2 S Me CH V7.05 CF₃ Et H 2 O Me N V7.06 CF₃ Et H2 S Me N V7.07 CF₃ Et H 2 O Me CH V7.08 CF₃ Et H 2 S Me CH V7.09 CF₃ EtCF₃ 2 NMe Me N 206-208 1.04 493 SQD13 V7.10 CF₃ Et CF₃ 2 NMe Me CH210-212 1.02 492 SDQ13 V7.11 CF₃ Et H 2 NMe Me N 152-154 0.87 425 ZQD13V7.12 CF₃ Et H 2 NMe Me CH 234-236 0.90 424 SQD13

TABLE V8 Compounds of the formula A5.1-B1.1: (A5.1-B1.1)

Ret. time No. R₅₂ R₅₁ R₅₀ m G₂₅ G₅₅ V₁₁ Mpt. (mins) (M + H) Method V8.01CF₃ Et CF₃ 2 CH N N V8.02 CF₃ Et CF₃ 2 CH N CH V8.03 CF₃ Et H 2 CH N NV8.04 CF₃ Et H 2 CH N CH V8.05 CF₃ Et CF₃ 2 N N N V8.06 CF₃ Et CF₃ 2 N NCH V8.07 CF₃ Et H 2 N N N V8.08 CF₃ Et H 2 N N CH V8.09 CF₃ Et CF₃ 2 CHCMe N V8.10 CF₃ Et CF₃ 2 CH CMe CH V8.11 CF₃ Et H 2 CH CMe N V8.12 CF₃Et H 2 CH CMe CH

TABLE V9 Compounds of the formula A5.1-B7.1: (A5.1-B7.1)

Ret. time No. R₅₂ R₄₁ R₄₂ m G₂₅ G₅₅ V₈₂ Mpt. ° C. (mins) (M + H) MethodV9.01 CF₃ Et CF₃ 2 CH N CH V9.02 CF₃ Et CF₃ 2 N N CH V9.03 CF₃ Et CF₃ 2N CMe CH

TABLE V10 Compounds of the formula A5.1-B9.1: (A5.1-B9.1)

Ret. time No. R₅₂ R₄₃ R₄₄ m G₂₅ G₅₅ V₈₁ Mpt. ° C. (mins) (M + H) MethodV10.01 CF₃ Et CF₃ 2 CH N CH V10.02 CF₃ Et CF₃ 2 N N CH V10.03 CF₃ Et CF₃2 N CMe CH V10.04 CF₃ Et CF₃ 2 CH N N V10.05 CF₃ Et CF₃ 2 N N N V10.06CF₃ Et CF₃ 2 N CMe N

TABLE VII Compounds of the formula A5.1-B11.1: (A5.1-B11.1)

Ret. time No. R₅₂ R₄₅ R₄₆ m G₂₅ G₅₅ Mpt. ° C. (mins) (M + H) MethodV11.01 CF₃ Et CF₃ 2 CH N V11.02 CF₃ Et CF₃ 2 N N V11.03 CF₃ Et CF₃ 2 NCMe

TABLE V12 Compounds of the formula A6.1-B1.1: (A6.1-B1.1)

No. R₅₄ R₅₁ R₅₀ m G₂₆ G₃₆ V₁₁ Mpt. ° C. Ret. time (mins) (M + H) MethodV12.01 CF₃ Et CF₃ 2 CH NMe N 214-216 0.99 439 ZQD13 V12.02 CF₃ Et CF₃ 2CH NMe CH 168-170 0.98 438 ZQD13 V12.03 CF₃ Et H 2 CH NMe N 211-213 0.81371 ZQD13 V12.04 CF₃ Et H 2 CH NMe CH 192-195 V12.05 CF₃ Et CF₃ 2 CH O N1.02 426 SQD13 V12.06 CF₃ Et CF₃ 2 CH O CH 1.04 423 SQD13 V12.07 CF₃ EtH 2 CH O N 0.87 358 SQD13 V12.08 CF₃ Et H 2 CH O CH V12.09 CF₃ Et CF₃ 2CH S N V12.10 CF₃ Et CF₃ 2 CH S CH V12.11 CF₃ Et H 2 CH S N V12.12 CF₃Et H 2 CH S CH V12.13 CF₃ Et CF₃ 2 N NMe N V12.14 CF₃ Et CF₃ 2 N NMe CHV12.15 CF₃ Et H 2 N NMe N V12.16 CF₃ Et H 2 N NMe CH V12.17 Cl Et CF₃ 2N NMe N 228-229 0.91 406/408 ZCQ13 V12.18 CF₃ Me CF₃ 2 CH NMe N 234-2360.93 425 SQD13 V12.19 CF₃ Et OCHF2 2 CH NMe N 146-148 1.03 405 SQD13V12.20 Br Et CF₃ 2 CH NMe N 188-190 0.95 449/451 SQD13

TABLE V13 Compounds of the formula A6.1-B7.1: (A6.1-B7.1)

No. R₅₄ R₄₁ R₄₂ m G₂₆ G₃₆ V₈₂ Mpt. ° C. Ret. time (mins) (M + H) MethodV13.01 CF₃ Et CF₃ 2 CH NMe CH 188-191 V13.02 CF₃ Et CF₃ 2 CH O CH V13.03CF₃ Et CF₃ 2 N NMe CH V13.04 CF₃ Et CF₃ 2 CH S CH V13.05 CF₃ Et H 2 CHNMe N 178-179 0.85 377 SQD13

TABLE V14 Compounds of the formula A6.1-B9.1: (A6.1-B9.1)

No. R₅₄ R₄₃ R₄₄ m G₂₆ G₃₆ V₈₁ Mpt. ° C. Ret. time (mins) (M + H) MethodV14.01 CF₃ Et CF₃ 2 CH NMe CH 115-117 1.09 407 SQD13 V14.02 CF₃ Et CF₃ 2CH O CH V14.03 CF₃ Et CF₃ 2 N NMe CH V14.04 CF₃ Et CF₃ 2 CH S CH V14.05CF₃ Et CF₃ 2 CH NMe N 168-170 0.95 445 SQD13 V14.06 CF₃ Et CF₃ 2 CH O NV14.07 CF₃ Et CF₃ 2 N NMe N V14.08 CF₃ Et CF₃ 2 CH S N

TABLE V15 Compounds of the formula A6.1-B11.1: (A6.1-B11.1)

No. R₅₄ R₄₅ R₄₆ m G₂₆ G₃₆ Mpt. ° C. Ret. time (mins) (M + H) MethodV15.01 CF₃ Et CF₃ 2 CH NMe 209-211 1.09 407 SQD13 V15.02 CF₃ Et CF₃ 2 CHO V15.03 CF₃ Et CF₃ 2 N NMe V15.04 CF₃ Et CF₃ 2 CH S

TABLE V16 Compounds of the formula A7.1-B1.1: (A7.1-B1.1)

No. R₅₆ R₅₁ R₅₀ m G₅₇ V₁₁ Mpt. ° C. Ret. time (mins) (M + H) MethodV16.01 CF₃ Et CF₃ 2 CMe N  240-242° 1.01 439 SQD13 V16.02 CF₃ Et CF₃ 2CH N 180-181 0.98 425 SQD13 V16.03 CF₃ Et CF₃ 2 N N 190-192 0.94 426SQD13 V16.04 CF₃ Et CF₃ 2 CMe CH V16.05 CF₃ Et CF₃ 2 CH CH 1.02 424SQD13 V16.06 CF₃ Et CF₃ 2 N CH 148-150 0.87 357 SQD13 V16.07 CF₃ Et H 2CMe N 0.81 371 SQD13 V16.08 CF₃ Et H 2 CH N 216-217 0.79 357 SQD13V16.09 CF₃ Et H 2 N N 0.76 358 SQD13 V16.10 CF₃ Et H 2 CMe CH V16.11 CF₃Et H 2 CH CH 166-167 0.88 356 SQD13 V16.12 CF₃ Et H 2 N CH 193-195 1.01425 SQD13

TABLE V17 Compounds of the formula A7.1-B7.1: (A7.1-B7.1)

No. R₅₆ R₄₁ R₄₂ m G₅₇ V₈₂ Mpt. ° C. Ret. time (mins) (M + H) MethodV17.01 CF₃ Et CF₃ 2 CMe CH V17.02 CF₃ Et CF₃ 2 H CH V17.03 CF₃ Et CF₃ 2N CH V17.04 CF₃ Et H 2 H N

TABLE V18 Compounds of the formula A7.1-B9.1: (A7.1-B9.1)

No. R₅₆ R₄₃ R₄₄ m G₅₇ V₈₁ Mpt. ° C. Ret. time (mins) (M + H) MethodV18.01 CF₃ Et CF₃ 2 CMe CH V18.02 CF₃ Et CF₃ 2 H CH 201-202° C. 1.08 430SQD13 V18.03 CF₃ Et CF₃ 2 N CH 161-162 1.04 431 SQD13 V18.04 CF₃ Et CF₃2 CMe N V18.05 CF₃ Et CF₃ 2 H N 163-165 1.06 431 SQD13 V18.06 CF₃ Et CF₃2 N N 157-158 0.97 432 SQD13

TABLE V19 Compounds of the formula A7.1-B11.1: (A7.1-B11.1)

No. R₅₆ R₄₅ R₄₆ m G₅₇ Mpt. °. Ret. time (mins) (M + H) Method V19.01 CF₃Et CF₃ 2 CMe V19.02 CF₃ Et CF₃ 2 CH 0.99 425 SQD13 V19.03 CF₃ Et CF₃ 2 N0.94 426 SQD13

TABLE V20 Compounds of the formula A8.1-B1.1: (A8.1-B1.1)

No. R₅₈ R₅₁ R₅₀ m G₄₈ V₁₁ Mpt. ° C. Ret. time (mins) (M + H) MethodV20.01 CF₃ Et CF₃ 2 CMe N 245-246 1.00 439 SQD13 V20.02 CF₃ Et CF₃ 2 CHN 197-203 0.97 425 SQD13 V20.03 CF₃ Et CF₃ 2 N N V20.04 CF₃ Et CF₃ 2 CMeCH V20.05 CF₃ Et CF₃ 2 CH CH 1.00 424 SQD13 V20.06 CF₃ Et CF₃ 2 N CHV20.07 CF₃ Et H 2 CMe N 272-273 0.80 371 SQD13 V20.08 CF₃ Et H 2 CH N208-218 0.77 357 ZCQ13 V20.09 CF₃ Et H 2 N N V20.10 CF₃ Et H 2 CMe CHV20.11 CF₃ Et H 2 CH CH V20.12 CF₃ Et H 2 N CH

TABLE V21 Compounds of the formula A8.1-B7.1: (A8.1-B7.1)

No. R₅₈ R₄₁ R₄₂ m G₄₈ V₈₂ Mpt. ° C. Ret. time (mins) (M + H) MethodV21.01 CF₃ Et CF₃ 2 CMe CH V21.02 CF₃ Et CF₃ 2 CH CH V21.03 CF₃ Et CF₃ 2N CH

TABLE V22 Compounds of the formula A8.1-B9.1: (A8.1-B9.1)

No. R₅₈ R₄₃ R₄₄ m G₄₈ V₈₁ Mpt. ° C. Ret. time (mins) (M + H) MethodV22.01 CF₃ Et CF₃ 2 C—Me CH V22.02 CF₃ Et CF₃ 2 CH CH 204-205 1.07 430SQD13 V22.03 CF₃ Et CF₃ 2 N CH V22.04 CF₃ Et CF₃ 2 CMe N V22.05 CF₃ EtCF₃ 2 CH N V22.06 CF₃ Et CF₃ 2 N N

TABLE V23 Compounds of the formula A8.1-B11.1: (A8.1-B11.1)

No. R₅₈ R₄₅ R₄₆ m G₄₈ Mpt. ° C. Ret. time (mins) (M + H) Method V23.01CF₃ Et CF₃ 2 CMe V23.02 CF₃ Et CF₃ 2 CH 0.98 425 SQD13 V23.03 CF₃ Et CF₃2 N

TABLE V24 Compounds of the formula A4.1-B7.1: (A4.1-B7.1)

No. R₄₈ R₄₁ m J₃ R₄₉ R₄₂ V₈₂ Mpt. ° C. Ret. time (mins) (M + H) MethodV24.01 CF₃ Et 2 O Me CF₃ CH V24.02 CF₃ Et 2 S Me CF₃ CH V24.03 CF₃ Et 2NMe Me CF₃ CH V24.04 CF₃ Et 2 NMe Me CF₃ CH 185-187 1.06 498 SQD13V24.05 CF₃ Et 2 Me Me H N 214-216 0.90 431 SQD13

TABLE V25 Compounds of the formula A4.1-B9.1: (A4.1-B9.1)

No. R₄₈ R₄₃ R₄₄ m J₃ R₄₉ V₈₁ Mpt. ° C. Ret. time (mins) (M + H) MethodV25.01 CF₃ Et CF₃ 2 O Me CH V25.02 CF₃ Et CF₃ 2 S Me CH V25.03 CF₃ EtCF₃ 2 NMe Me CH 158-160 1.03 498 SQD13 V25.04 CF₃ Et CF₃ 2 O Me N V25.05CF₃ Et CF₃ 2 S Me N V25.06 CF₃ Et CF₃ 2 NMe N 170-172 0.99 499 SQ13

TABLE V26 Compounds of the formula A4.1-B11.1: (A4.1-B11.1)

No. R₄₈ R₄₅ R₄₆ m J₃ R₄₉ Mpt. ° C. Ret. time (mins) (M + H) MethodV26.01 CF₃ Et CF₃ 2 O Me V26.02 CF₃ Et CF₃ 2 S Me V26.03 CF₃ Et CF₃ 2NMe Me 197-199 0.95 493 SQD13

Formulation Examples (%=Percent by Weight)

Example F1: Emulsion concentrates a) b) c) Active ingredient 25% 40% 50%Calcium dodecylbenzenesulfonate  5%  8%  6% Castor oil polyethylene  5%— — glycol ether (36 mol of EO) Tributylphenoxypolyethylene glycol — 12% 4% ether (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture 65% 25%20%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

Example F2: Solutions a) b) c) d) Active ingredient 80% 10% 5% 95%Ethylene glycol monomethyl 20% — — — ether Polyethylene glycol — 70% — —MW 400 N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1% 5% Petroleum ether — — 94%  — (boiling range: 160-190°)

The solutions are suitable for use in the form of microdrops.

Example F3: Granules a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin94%  — 79% 54% Highly disperse silica 1% — 13%  7% Attapulgite — 90% —18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier(s), and the solvent is subsequently evaporatedin vacuo.

Example F4: Dusts a) b) Active ingredient 2% 5% Highly disperse silica1% 5% Talc 97%  — Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers andthe active ingredient.

Example F5: Wettable powders a) b) c) Active ingredient 25%  50% 75%Sodium lignosulfonate 5%  5% — Sodium lauryl sulfate 3% —  5% Sodiumdiisobutyl- —  6% 10% naphthalenesulfonate Octylphenoxypolyethyleneglycol —  2% — ether (7-8 mol of EO) Highly disperse silica 5% 10% 10%Kaolin 62%  27% —

The active ingredient is mixed with the additives and the mixture isground thoroughly in a suitable mill. This gives wettable powders, whichcan be diluted with water to give suspensions of any desiredconcentration.

Example F6: Extruder Granules

Active ingredient 10% Sodium lignosulfonate  2% Carboxymethylcellulose 1% Kaolin 87%

The active ingredient is mixed with the additives, and the mixture isground, moistened with water, extruded, granulated and dried in a streamof air.

Example F7: Coated Granules

Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94% 

In a mixer, the finely ground active ingredient is applied uniformly tothe kaolin, which has been moistened with the polyethylene glycol. Thisgives dust-free coated granules.

Example F8: Suspension Concentrate

Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethyleneglycol ether (15 mol of EO)  6% Sodium lignosulfonate 10%Carboxymethylcellulose  1% 37% aqueous formaldehyde solution 0.2% Silicone oil (75% aqueous emulsion) 0.8%  Water 32%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

Example F9: Powders for dry seed treatment a) b) c) active ingredient25% 50% 75% light mineral oil  5%  5%  5% highly dispersed silicic acid 5%  5% — Kaolin 65% 40% — Talcum — — 20%

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Example F10: Emulsifiable Concentrate

active ingredient 10% octylphenol polyethylene glycol ether (4-5 mol ofethylene  3% oxide) calcium dodecylbenzenesulfonate  3% castor oilpolyglycol ether (35 mol of ethylene oxide)  4% Cyclohexanone 30% xylenemixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Example F11: Flowable Concentrate for Seed Treatment

active ingredients 40%  propylene glycol 5% copolymer butanol PO/EO 2%Tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (inthe form of a 20% solution in 0.5%  water) monoazo-pigment calcium salt5% Silicone oil (in the form of a 75% emulsion in water) 0.2%  Water45.3%  

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use.

Suitable additions to active ingredients here are, for example,representatives of the following classes of active ingredients:organophosphorus compounds, nitrophenol derivatives, thioureas, juvenilehormones, formamidines, benzophenone derivatives, ureas, pyrrolederivatives, carbamates, pyrethroids, chlorinated hydrocarbons,acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoidsand Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds described in Tables1 to 168 and V1 to V26 of the present invention”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX,an acaricide selected from the group of substances consisting ofacequinocyl ([57960-19-7] [CCN])+TX, fenpyroxymate[134098-61-6][CCN]+TX, flucythrinate [70124-77-5][CCN]+TX,1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,hexythiazox [78587-05-0][CCN]+TX, 2,4-dichlorophenyl benzenesulfonate(IUPAC/Chemical Abstracts name) (1059)+TX,2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295)+TX,4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX, abamectin (1)+TX,acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin (202)+TX, amidithion(870)+TX, amidoflumet [CCN]+TX, amidothioate (872)+TX, amiton (875)+TX,amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, aramite (881)+TX,arsenous oxide (882)+TX, AVI 382 (compound code)+TX, AZ 60541 (compoundcode)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azobenzene(IUPAC name) (888)+TX, azocyclotin (46)+TX, azothoate (889)+TX, benomyl(62)+TX, benoxafos (alternative name) [CCN]+TX, benzoximate (71)+TX,benzyl benzoate (IUPAC name) [CCN]+TX, bifenazate (74)+TX, bifenthrin(76)+TX, binapacryl (907)+TX, brofenvalerate (alternative name)+TX,bromo-cyclen (918)+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX,bromopropylate (94)+TX, buprofezin (99)+TX, butocarboxim (103)+TX,butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, calciumpolysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate(943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbophenothion(947)+TX, CGA 50′439 (development code) (125)+TX, chinomethionat(126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX, chlordimeformhydrochloride (964)+TX, chlorfenapyr (130)+TX, chlorfenethol (968)+TX,chlorfenson (970)+TX, chlorfensulfide (971)+TX, chlorfenvinphos(131)+TX, chlorobenzilate (975)+TX, chloromebuform (977)+TX,chloromethiuron (978)+TX, chloropropylate (983)+TX, chlorpyrifos(145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, cinerinI (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofentezine(158)+TX, closantel (alternative name) [CCN]+TX, coumaphos (174)+TX,crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb(1013)+TX, cyanthoate (1020)+TX, cyflumetofen [400882-07-7]+TX,cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM(1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O (1037)+TX,demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX,demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX,demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX,diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX,dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternativename)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX,dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name)(653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton(269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX,dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX,dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPACname) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton(278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternativename) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX,eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX,ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX,fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternativename)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil(1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim(360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron(366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron(370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate(1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX,formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate(1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX,heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/ChemicalAbstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPACname) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX,malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan(1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX,methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX,mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX,milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512(compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternativename) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloridecomplex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compoundcode)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX,oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX,permethrin (626)+TX, petroleum oils (alternative name) (628)+TX,phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX,phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes(traditional name) (1347)+TX, polynactins (alternative name) (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name)[CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen(738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX,sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep(753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX,tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam(alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox(alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX,thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternativename) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos(820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion(847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name)[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin(alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX,milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternativename) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name)[CCN]+TX, spinosad (737) and thiophanate (1435)+TX,an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericideselected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX,a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX,an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure Ill(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX,an insect repellent selected from the group of substances consisting of2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX, an insecticide selected from thegroup of substances consisting of momfluorothrin [609346-29-4]+TX,pyrafluprole [315208-17-4]+TX, flometoquin [875775-74-9]+TX,flupyradifuron [951659-40-8]+TX, 1-dichloro-1-nitroethane(IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX,alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX,aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate(872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin(alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (alternative name) (52)+TX, bariumhexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide(IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin(76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer(alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin(908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name)(909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate(alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX,bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbondisulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride(IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX,cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternativename) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, E1 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name)(473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion(480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I(alternative name) [CCN]+TX, juvenile hormone II (alternative name)[CCN]+TX, juvenile hormone Ill (alternative name) [CCN]+TX, kelevan(1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, leadarsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane(430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion(1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesiumphosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben(1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX,menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX,mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX,metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX,methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride(IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX,methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX,methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternativename) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methylbromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform(alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene Ill (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin 1 (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX, cyantraniliprole [736994-63-19]+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX and a compound ofthe formula B1E

with the common name triflumezopyrim (disclosed in WO 2012/092115)+TX; amolluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX,a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX,carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX,cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet(216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX, fluensulfone [318290-98-1]+TX, a nitrification inhibitorselected from the group of substances consisting of potassiumethylxanthate [CCN] and nitrapyrin (580)+TX,a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX, a virucide selected from the group of substances consisting ofimanin (alternative name) [CCN] and ribavirin (alternative name)[CCN]+TX,a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,and biologically active compounds selected from the group consisting ofazaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole[116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole[119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole[106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole[136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol[76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX,imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole[125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate[101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole[178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX,propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX,tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX,triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl[71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX,R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX,debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline[24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX,procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide[130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3][112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin[131860-33-8]+TX, mandestrobin [173662-97-0]+TX, dimoxystrobin[149961-52-4]+TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003,1, 93}+TX, fluoxastrobin [361377-29-9]+TX, kresoxim-methyl[143390-89-0]+TX, metomi-nostrobin [133408-50-1]+TX, trifloxystrobin[141517-21-7]+TX, orysastrobin [248593-16-0]+TX, picoxystrobin[117428-22-5]+TX, pyraclostrobin [175013-18-0]+TX, ferbam[14484-64-1]+TX,3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine (SYP-Z048),mancozeb [8018-01-7]+TX, maneb [12427-38-2]+TX, metiram [9006-42-2]+TX,propineb [12071-83-9]+TX, thiram [137-26-8]+TX, zineb [12122-67-7]+TX,ziram [137-30-4]+TX, captafol [2425-06-1]+TX, captan [133-06-2]+TX,dichlofluanid [1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet[133-07-3]+TX, tolylfluanid [731-27-1]+TX, bordeaux mixture[8011-63-0]+TX, copperhydroxid [20427-59-2]+TX, copperoxychlorid[1332-40-7]+TX, coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX,mancopper [53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap[131-72-6]+TX, nitrothal-isopropyl [10552-74-6]+TX, edifenphos[17109-49-8]+TX, iprobenphos [26087-47-8]+TX, isoprothiolane[50512-35-1]+TX, phosdiphen [36519-00-3]+TX, pyrazophos [13457-18-6]+TX,tolclofos-methyl [57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX,anilazine [101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX,chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX,diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb[87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-L190 (Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX,etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone[161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX,ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol[10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb[66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron[66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX,probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid[189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen[124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX,tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole[41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX,zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX, andSDHI inhibitors selected from the group consisting of penflufen([494793-67-8], U.S. Pat. No. 7,538,073(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide)+TX,furametpyr ([123572-88-3](5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-1H-pyrazole-4-carboxamide)+TX,penthiopyrad (U.S. Pat. No. 5,747,518, [183675-82-3],(N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide)+TX,bixafen (U.S. Pat. No. 7,329,633, [581809-46-3],(N-(3′,4′-dichloro-5-fluoro[1,1′-biphenyl]-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide)+TX,isopyrazam (U.S. Pat. No. 7,598,395, [881685-58-1] (mixture of 2syn-isomers3-(difluoromethyl)-1-methyl-N-[(1RS,4SR,9RS)-1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl]pyrazole-4-carboxamideand 2 anti-isomers3-(difluoromethyl)-1-methyl-N-[(1RS,4SR,9SR)-1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl]pyrazole-4-carboxamide)+TX,sedaxane (EP 1480955B1, [874967-67-6](mixture of 2 cis-isomers2′-[(1RS,2RS)-1,1′-bicycloprop-2-yl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxanilideand 2 trans-isomers2′-[(1RS,2SR)-1,1′-bicycloprop-2-yl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxanilide)+TX,fluxapyroxad (U.S. Pat. No. 8,008,232, [907204-31-3](3-(difluoromethyl)-1-methyl-N-(3′,4′,5′-trifluoro[1,1′-biphenyl]-2-yl)-1H-pyrazole-4-carboxamide)+TX,solatenol (WO 2007/048556(3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide)+TX,the compound3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide(described in WO 2010/063700)+TX, thifluzamide (U.S. Pat. No. 5,045,554,[130000-40-7](N-[2,6-dibromo-4-(trifluoromethoxy)phenyl]-2-methyl-4-(trifluoromethyl)-5-thiazolecarboxamide)+TX,boscalid (U.S. Pat. No. 5,589,493, [188425-85-6(2-chloro-N-(4′-chloro[1,1′-biphenyl]-2-yl)-3-pyridinecarboxamide)+TX,oxycarboxin ([5259-88-1](5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide4,4-dioxide)+TX, carboxin ([5234-68-4](5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide)+TX, fluopyram(U.S. Pat. No. 7,572,818, [658066-35-4],(N-[2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl]-2-(trifluoromethyl)benzamide)+TX,flutolanil ([24691-80-3], (2-methyl-N-phenyl-3-furancarboxamide,fenfuram), U.S. Pat. No. 4,093,743, CA Reg. No. 66332-96-5(N-[3-(1-methylethoxy)phenyl]-2-(trifluoromethyl)benzamide)+TX, mepronil([55814-41-0], (2-methyl-N-[3-(1-methylethoxy)phenyl]benzamide)+TX andbenodanil ([15310-01-7], (2-iodo-N-phenylbenzamide)+TX;and the compounds[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX,1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX and 4-oxo-4-[(2-phenylethyl)amino]-butyric acid(disclosed in WO 2010/137677)+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright © 1995-2013]; for example, thecompound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed.

The active ingredient mixture of the compounds of formula I selectedfrom Tables 1 to 168 and V1 to V26 with active ingredients describedabove comprises a compound selected from Tables 1 to 130 and an activeingredient as described above preferably in a mixing ratio of from 100:1to 1:6000, especially from 50:1 to 1:50, more especially in a ratio offrom 20:1 to 1:20, even more especially from 10:1 to 1:10, veryespecially from 5:1 and 1:5, special preference being given to a ratioof from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewisepreferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4,or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5,or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75,or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750,or 2:750, or 4:750. Those mixing ratios are ratios by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from Tables 1to 168 and V1 to V26 and one or more active ingredients as describedabove can be applied, for example, in a single “ready-mix” form, in acombined spray mixture composed from separate formulations of the singleactive ingredient components, such as a “tank-mix”, and in a combineduse of the single active ingredients when applied in a sequentialmanner, i.e. one after the other with a reasonably short period, such asa few hours or days. The order of applying the compounds of formula Iselected from Tables 1 to 168 and V1 to V26 and the active ingredientsas described above is not essential for working the present invention.

BIOLOGICAL EXAMPLES Example B1: Spodoptera littoralis (Egyptian CottonLeaf Worm)

Test compounds were applied by pipette from 10′000 ppm DMSO stocksolutions into 24-well plates and mixed with agar. Lettuce seeds wereplaced on the agar and the multi well plate was closed by another platewhich contains also agar. After 7 days the roots have absorbed thecompound and the lettuce has grown into the lid plate. The lettuce leafswere now cut off into the lid plate. Spodoptera eggs were pipettedthrough a plastic stencil on a humid gel blotting paper and the plateclosed with it. The samples were assessed for mortality, anti-feedanteffect and growth inhibition in comparison to untreated samples 6 daysafter infestation.

The following compounds gave an effect of at least 80% in at least oneof the three categories (mortality, anti-feedancy, or growth inhibition)at a test rate of 12.5 ppm:

V20.02, V20.01, V16.02, V12.02, V16.01, V12.01, and V12.03

Example B2: Spodoptera littoralis (Egyptian Cotton Leaf Worm)

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10′000 ppm DMSO stocksolutions. After drying the leaf discs were infested with five L1larvae. The samples were assessed for mortality 3 days afterinfestation. The following compounds resulted in at least 80% mortalityat an application rate of 200 ppm: The following compounds resulted inat least 80% control at an application rate of 200 ppm:

V14.01, V12.18, V16.08, V20.02, V16.02, V12.20, V12.02, V16.01, V12.01,V7.11, V12.03, V25.03 and V7.09

Example B3: Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10′000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (10 to15 per well). The samples were assessed for mortality 5 days afterinfestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

V14.01, V16.08, V20.08, V20.02, V16.09, V16.03, V16.07, V16.02, V12.02,V16.01, V12.01, V7.11, V12.03, V13.05, V25.03 and V7.09

Example B4: Diabrotica balteata (Corn Root Worm)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10′000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (6 to10 per well). The samples were assessed for mortality and growthinhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm:

V14.01, V12.18, V16.08, V20.02, V16.09, V16.03, V16.07, V16.02, V12.20,V12.02, V12.01, V7.11, V12.03, V13.05, V25.03 and V7.09.

Example B5: Myzus persicae (Green Peach Aphid)

Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions. After drying, the leaf discs were infested with anaphid population of mixed ages. The samples were assessed for mortality6 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

V14.01, V16.08, V20.08, V16.09, V16.03, V16.07, V16.02, V12.20, V12.02,V14.05, V16.01, V12.17, V12.01, V7.11, V12.03, V25.03 and V7.09.

Example B6: Myzus persicae (Green Peach Aphid)

Roots of pea seedlings infested with an aphid population of mixed ageswere placed directly in the aqueous test solutions prepared from 10,000DMSO stock solutions. The samples were assessed for mortality 6 daysafter placing seedlings in test solutions.

The following compounds resulted in at least 80% mortality at a testrate of 24 ppm:

V16.08, V20.08, V16.09, V16.03, V16.07, V12.20, V12.02, V14.05, V12.17,V12.01, and V12.03.

Example B7: Myzus persicae (Green Peach Aphid)

Test compounds from 10′000 ppm DMSO stock solutions were applied bypipette into 24-well microtiter plates and mixed with sucrose solution.The plates were closed with a stretched Parafilm. A plastic stencil with24 holes was placed onto the plate and infested pea seedlings wereplaced directly on the Parafilm. The infested plate was closed with agel blotting paper and another plastic stencil and then turned upsidedown. The samples were assessed for mortality 5 days after infestation.

The following compounds resulted in at least 80% mortality at a testrate of 12 ppm:

V12.20, V12.02, V14.05, V16.01, V12.17, V12.01, V7.11, V12.03, and V7.09

Example B8: Thrips tabaci (Onion Thrips)

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions. After drying the leaf discs were infested with a thripspopulation of mixed ages. The samples were assessed for mortality 6 daysafter infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

V12.01, V12.03, and V7.09

Example B9: Frankliniella occidentalis (Western Flower Thrips)

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10′000 DMSO stocksolutions. After drying the leaf discs were infested with aFrankliniella population of mixed ages. The samples were assessed formortality 7 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

V12.02

Example B10: Bemisia tabaci (Cotton White Fly)

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10′000 ppm DMSO stocksolutions. After drying the leaf discs were infested with adult whiteflies. The samples were checked for mortality 6 days after incubation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

V12.20, V12.02, V12.01, V13.05, V25.03 and V7.09.

Example B11: Tetranychus urticae (Two-Spotted Spider Mite)

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10,000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

V14.01, V12.18, V20.08, and V16.02.

Example B12: Aedes aegypti (Yellow Fever Mosquito)

larvicide, contact/feeding activity, curative

10 to 15 Aedes larvae (L2) together with a nutrition mixture were placedin 96-well microtiter plates.

Test compounds were pipetted into the wells. After an incubation periodof 2 days insects were assessed for mortality and growth inhibition.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at a test rate of5 ppm:

V12.01

What is claimed is:
 1. A compound of formula I,A-B  (I), wherein A is a radical selected from the group consisting offormulae A₁ to A₈:

wherein the arrow denotes the point of attachment to the radical B; andB is a radical selected from the group consisting of formulae B₁ to B₁₁:

wherein the arrow denotes the point of attachment to the radical A;wherein L₁ is methylene or a direct bond; V₀ nitrogen or CR₅; V₁ isnitrogen or CR₂₀; V₂ is nitrogen or CR₂₁; V₃ is nitrogen or CR₂₂; V₄ isnitrogen or CR₂₃; V₅ is nitrogen or CR₂₄; V₅ is nitrogen or CR₂₅; V₇ isnitrogen or CR₂₆; V₈ is nitrogen or CR₂₇; V₉ is nitrogen, or CR₂₈; V₁₀is nitrogen or CR₂₉; V₁₁ is nitrogen or CR₃₀; G₁ is nitrogen or CR₃₁; G₂is nitrogen or CR₃₂; G₃ is —NR₃₅, an oxygen atom or a sulphur atom; G₄is nitrogen or CR₃₃; G₅ is nitrogen or CR₃₄; J₁, J₂, J₃ together formtogether a 5 membered heterocyclic ring, which can be saturated orunsaturated, containing one or two atoms selected from the groupconsisting of nitrogen, oxygen and sulphur, which ring can be mono- orpolysubstituted by substituents selected from the group consisting ofC₁-C₆alkyl, halogen and or C₁-C₆haloalkyl, with the proviso that if thering contains two oxygen atoms, or two sulphur atoms, they are separatedby one carbon atom; R₁ and R₂ are the same or different and eachrepresents, hydrogen, halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; R₃ is aC₁-C₆alkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl group which can be mono- orpolysubstituted by substituents selected from the group consisting ofC₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy,C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy, C₁-C₆alkylsulphanyl,C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl, C₁-C₆haloalkylsulphinyl,C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,cyano, hydroxy, halogen, C₃-C₆cycloalkyl, said C₃-C₆cycloalkyl itselfcan be mono- or polysubstituted by substituents selected from halogenand C₁-C₃alkyl; and by a 5- or 6-membered heterocyclic group, which canbe mono- or polysubstituted by substituents selected from the groupconsisting of C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl,C₁-C₆haloalkylsulphinyl, C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl,C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl,C₂-C₆haloalkoxycarbonyl, C₁-C₆alkylamino, C₁-C₆haloalkylamino,C₂-C₈dialkylamino, C₂-C₈halodialkylamino, halogen, cyano and nitro; orR₃ is C₃-C₆cycloalkyl, which can be mono- or polysubstituted bysubstituents selected from the group consisting of C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy and halogen;or R₃ is a 5- or 6-membered heterocyclic group, which can be mono- orpolysubstituted by substituents selected from the group consisting ofC₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl,C₁-C₆haloalkylsulphinyl, C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl,C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl,C₂-C₆haloalkoxycarbonyl, C₁-C₆alkylamino, C₁-C₆haloalkylamino,C₂-C₈dialkylamino, C₂-C₈halodialkylamino, halogen, cyano and nitro; orR₃ is —CO₂R₃₆, —C(O)R₃₆ or hydrogen; R₃₅ is hydrogen, C₁-C₆alkyl whichcan be mono- or polysubstituted by substituents selected from the groupconsisting of C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆ alkynyloxy, C₂-C₆haloalkynyloxy,C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl,C₁-C₆haloalkylsulphinyl, C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl,C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, cyano, hydroxy, halogen andC₃-C₆cycloalkyl, said C₃-C₆cycloalkyl itself can be mono- orpolysubstituted by substituents selected from halogen and C₁-C₃alkyl; oran N-oxide thereof; R₄, R₅, R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈,R₂₉, and R₃₀ are the same or different and represents cyano, nitro,halogen, hydroxy, C₁-C₆alkenyloxy, C₁-C₅-haloalkoxy, C₃-C₆cycloalkyl,—C(O)R₃₆ or hydrogen; or C₁-C₆alkyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofcyano, halogen, hydroxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy,C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulphanyl, C₁-C₆ alkylsulphinyl,C₁-C₆haloalkylsulphinyl, C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl,C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl,C₂-C₆haloalkoxycarbonyl, cyano, hydroxy, halogen and C₃-C₆cycloalkyl,said cycloalkyl itself can be substituted by substituents selected fromthe group consisting of halogen and C₁-C₃alkyl; or represents a phenylgroup which can be mono or polysubstituted by substituents selected fromthe group consisting of C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulphanyl,C₁-C₆alkylsulphinyl, C₁-C₆haloalkylsulphinyl, C₁-C₆alkylsulphonyl,C₁-C₆haloalkylsulphonyl, C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl, C₁-C₆alkylamino,C₁-C₆haloalkylamino, C₂-C₈dialkylamino, C₂-C₈halodialkylamino, halogen,cyano, and nitro; R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆,R₁₇, R₁₈ and R₁₉ are the same or different and represents C₁-C₆ alkyl,C₁-C₆ haloalkyl, or hydrogen, and the group CR₁₃R₁₄ can additionally bea carbonyl group C═O; R₃₁, R₃₂, R₃₃ and R₃₄ are the same or differentand represents C₁-C₆alkyl, C₁-C₆haloalkyl, —OR₇, —S(O)_(n)R₃₆, —NR₃₆R₃₇,—CO₂R₃₆,—C(O)R₃₆, cyano, nitro, halogen or hydrogen; R₃₆ and R₃₇ are thesame or different and represents hydrogen, C₁-C₆alkyl which can be mono-or polysubstituted by substituents selected from C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy,C₂-C₆haloalkynyloxy, C₁-C₆alkylsulphanyl, C₁-C₆haloalkylsulphanyl,C₁-C₆alkylsulphinyl, C₁-C₆haloalkylsulphinyl, C₁-C₆alkylsulphonyl,C₁-C₆haloalkylsulphonyl, C₂-C₆alkylcarbonyl, C₂-C₆haloalkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl, cyano, hydroxy, halogenand C₃-C₆ cycloalkyl, wherein said C₃-C₆ cycloalkyl can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen and C₁-C₃alkyl; or R₃₆ and R₃₇ are the same or different andrepresents a phenyl group which can be mono- or polysubstituted bysubstituents selected from the group consisting of C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulphanyl,C₁-C₆haloalkylsulphanyl, C₁-C₆alkylsulphinyl, C₁-C₆haloalkylsulphinyl,C₁-C₆alkylsulphonyl, C₁-C₆haloalkylsulphonyl, C₂-C₆alkylcarbonyl,C₂-C₆haloalkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆haloalkoxycarbonyl,C₁-C₆alkylamino, C₁-C₆haloalkylamino, C₂-C₈dialkylamino,C₂-C₈halodialkylamino, halogen, cyano, and nitro; each m independentlyrepresents 0, 1 or 2, and n represents 0, 1 or 2, with the proviso that:a) in —S(O)_(n)R₃₆, R₃₆ is hydrogen when n is 0; b) if B is 1, then A isdifferent from A2, A3 and A5; c) if A is A1, then B is different from 1,B7, B8, B9 and B10; d) if A is A₅, then B is different from B₁₀; or anagrochemically acceptable salt, enantiomer, diastereomer, tautomer, orN-oxide thereof.
 2. A compound of formula I according to claim 1,represented by the combinations of Radical A2 with radicals B selectedfrom B7, B9 and B11; wherein A2 is represented by the radical A2.1

wherein R₄₀ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl; G₂₁ is nitrogen, CH, C—C₁-C₆ alkyl,C—C₁-C₆haloalkyl, C-halogen, C—CN, C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl,C—SO₂—C₁-C₄alkyl, C—S-phenyl, C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; andG₅₁ is nitrogen, CH, C—C₁-C₆ alkyl, C—C₁-C₀₆haloalkyl, C-halogen, C—CN,C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl, C—SO₂—C₁-C₄alkyl, C—S-phenyl,C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; and the radicals B7, B9 and B11are represented by the radicals selected from B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2; V₈₂ is nitrogen or methine; R₄₁ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₁ is nitrogen or methine, R₄₃ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2; R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₄₆ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.
 3. A compound of formula I accordingto claim 1, represented by the combinations of Radical A3 with radicalsB selected from B7, B9 and B11; wherein A3 is represented by the radicalA3.1

wherein R₄₇ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl; G₄₁ is nitrogen, CH, C—C₁-C₆ alkyl,C—C₁-C₆haloalkyl, C-halogen, C—CN, C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl,C—SO₂—C₁-C₄alkyl, C—S-phenyl, C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; andG₂₂ is nitrogen, CH, C—C₁-C₆ alkyl, C—C₁-C₆haloalkyl, C-halogen, C—CN,C—O—C₁-C₄alkyl, C—S—C₁-C₄alkyl, C—SO₂—C₁-C₄alkyl, C—S-phenyl,C—SO₂-phenyl or C—SO₂—C₁-C₄halolakyl; and the radicals B7, B9 and B11are represented by the radicals selected from B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2; V₈₂ is nitrogen or methine; R₄₁ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₁ is nitrogen or methine, R₄₃ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2; R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₄₆ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.
 4. A compound of formula I accordingto claim 1, represented by the combinations of Radical A4 with radicalB1; wherein A4 is represented by the radical A4.1

wherein R₄₈ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl; J₃ is sulphur, oxygen or N-methyl; andR₄₉ is hydrogen, C₁-C₆ alkyl, C₁-C₆haloalkyl, halogen, CN, O—C₁-C₄alkyl,S—C₁-C₄alkyl, SO₂—C₁-C₄alkyl, S-phenyl, SO₂-phenyl orSO₂—C₁-C₄halolakyl; and the radical 1 is

wherein m is 0, 1 or 2; R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₅₀ is hydrogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.
 5. A compound of formula I accordingto claim 1, represented by the combinations of Radical A5 with radicalsB selected from 1, B7, B9 and B11; wherein A5 is represented by theradical A5.1

wherein G₅₅ is nitrogen or C—R₅₃; R₅₃ is C₁-C₄alkyl; G₂₅ is nitrogen ormethine; and R₅₂ is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio,mercapto or C₁-C₄alkoxycarbonyl; and the radicals B1, B7, B9 and B11 arerepresented by the radicals selected from B1.1, B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2; R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₅₀ is hydrogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₂ is nitrogen or methine; R₄₁ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₁ is nitrogen or methine; R₄₃ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2; R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₄₆ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.
 6. A compound of formula I accordingto claim 1, represented by the combinations of Radical A6 with radicalsB selected from 1, B7, B9 and B11; wherein A6 is represented by theradical A6.1

wherein G₃₆ is N—R₅₅, oxygen or sulfur; R₅₅ is C₁-C₄alkyl; G₂₆ isnitrogen or methine; and R₅₄ is halogen, C₁-C₄haloalkyl,C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅,phenylcarbonylthio, mercapto or C₁-C₄alkoxycarbonyl; and the radicalsB1, B7, B9 and B11 are represented by the radicals selected from B1.1,B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2; R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₅₀ is hydrogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₂ is nitrogen or methine; R₄₁ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₁ is nitrogen or methine, R₄₃ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2; R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₄₆ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.
 7. A compound of formula I accordingto claim 1, represented by the combinations of radical A7 with radicalsB selected from 1, B7, B9 and B11; wherein A7 is represented by theradical A7.1

wherein G₅₇ is nitrogen or C—R₅₇; R₅₇ is hydrogen or C₁-C₄alkyl; and R₅₆is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfonyl,O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio, mercapto orC₁-C₄alkoxycarbonyl; and the radicals B1, B7, B9 and B11 are representedby the radicals selected from B1.1, B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2; R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₅₀ is hydrogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₂ is nitrogen or methine; R₄₁ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₁ is nitrogen or methine; R₄₃ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2; R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₄₆ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.
 8. A compound of formula I accordingto claim 1, represented by the combinations of Radical A8 with radicalsB selected from 1, B7, B9 and B11; wherein A8 is preferably representedby the radical A8.1

wherein G₄₈ is nitrogen or C—R₅₉; R₅₉ is hydrogen or C₁-C₄alkyl; and R₅₈is halogen, C₁-C₄haloalkyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfonyl,O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio, mercapto orC₁-C₄alkoxycarbonyl; and the radicals B1, B7, B9 and B11 are preferablyrepresented by the radicals selected from B1.1, B7.1, B9.1 and B11.1

wherein m is 0, 1 or 2; R₅₁ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₅₀ is hydrogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₂ is nitrogen or methine; R₄₁ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₂ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl;

wherein m is 0, 1 or 2; V₈₁ is nitrogen or methine; R₄₃ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl,C₃-C₆halocycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; andR₄₄ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

wherein m is 0, 1 or 2; R₄₅ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and R₄₆ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₃haloalkoxy, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl or C₂-C₆alkynyl.
 9. A compound of formula I accordingto 1, wherein L₁, in reference to each of B, is a direct bond.
 10. Acompound of formula I according to 1, wherein R₁, in reference to eachof A, is the same or different and each represents hydrogen, halogen,C₁-C₃ alkyl or C₁-C₃ haloalkyl.
 11. A compound of formula I according to10, wherein R₂, in reference to each of A, is the same or different andeach represents hydrogen, halogen, C₁-C₃ alkyl or C₁-C₃haloalkyl.
 12. Acompound of formula I according to 10, wherein R₃, in reference to eachof B, is the same or different and each represents C₁-C₃ alkyl or C₁-C₃haloalkyl.
 13. A compound of formula I according to 10, wherein R₄, inreference to each of B, is the same or different and each representshydrogen or C₁-C₃ alkyl.
 14. An insecticidal, acaricidal, nematicidal ormolluscicidal composition, comprising an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compound offormula I according to claim 1 and a suitable carrier or diluenttherefor.
 15. A method of combating and controlling pests whichcomprises applying an insecticidally, acaricidally, nematicidally ormolluscicidally effective amount of a compound of formula I according toclaim 1 or a composition comprising a compound of formula I, to a pest,a locus of pest, or to a plant susceptible to attack by a pest, with theexception of a method for treatment of the human or animal body bysurgery or therapy and diagnostic methods practised on the human oranimal body.
 16. A method for the protection of plant propagationmaterial from the attack by pests, which comprises treating thepropagation material or the site, where the propagation material isplanted, with a composition according to claim
 14. 17. Plant propagationmaterial treated in accordance with the method described in claim 16.